US5145657A - Method for purification of gas - Google Patents

Method for purification of gas Download PDF

Info

Publication number
US5145657A
US5145657A US07/684,983 US68498391A US5145657A US 5145657 A US5145657 A US 5145657A US 68498391 A US68498391 A US 68498391A US 5145657 A US5145657 A US 5145657A
Authority
US
United States
Prior art keywords
component
tio
weight
ozone
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07/684,983
Inventor
Motonobu Kobayashi
Kiichiro Mitsui
Yoku Nanba
Toshihide Kanzaki
Kunio Sano
Takehiko Suzuki
Akira Inoue
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP62010008A external-priority patent/JPH0741146B2/en
Priority claimed from JP62011247A external-priority patent/JPS63181764A/en
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Application granted granted Critical
Publication of US5145657A publication Critical patent/US5145657A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/56—
    • B01J35/64—

Definitions

  • This invention relates to a method for the purification of a gas and a catalyst for use in the purification. More particularly, it relates to a method for catalytically decomposing ozone contained in a gas or catalytically decomposing a component of offensive odor in a gas through oxidation with ozone and to a catalyst used for the decomposition.
  • Ozone possesses a strong oxidizing ability and, on decomposition, converts itself into harmless oxygen. Thus, it has found extensive utility in various applications aimed at deodorizing, sterilizing, and bleaching various substances and even lowering the COD level of plant effluents.
  • the stray ozone has the possibility of giving rise to secondary environmental pollution such as, for example, generation of a photochemical smog.
  • secondary environmental pollution such as, for example, generation of a photochemical smog.
  • the air containing ozone is drawn into the interior of the airplane, the passengers and the crew aboard the airplane may possibly be exposed to the adverse effect of the ozone in the air.
  • the odor of ozone can be perceived even when the ozone is present in a concentration of not more than 1 ppm.
  • ozone When ozone is present in the air in a concentration exceeding 2 ppm, it stimulates the respiratory system of a person inhaling the air and does harm to the person's body.
  • the air which contains the ozone issuing from a varying ozone sources must be detoxified by removal of the ozone.
  • the method using activated carbon As conventional techniques used for disposal of spent ozone, the method using activated carbon, the method using a liquid detergent, and the method resorting to thermal decomposition have been available
  • the activated carbon method When the activated carbon method is utilized for the treatment of air containing ozone in a low concentration, the activated carbon must be replenished as it is consumed in consequence of progress of the decomposition of ozone.
  • this method When this method is used for the treatment of air containing ozone in a high concentration, the activated carbon must be handled attentively because it has the possibility of being ignited and burnt by the heat of reaction.
  • the liquid detergent method resides in purifying air containing spent ozone with the aqueous solution of a reducing substance. Thus, the treatment costs much and gives rise to a problem of waste water disposal.
  • the thermal decomposition method has the disadvantage that it requires application of heat to a temperature of not less than 300° C. for the purpose of enhancing the efficiency of decomposition, necessitates an expensive application of heat for the disposal of a large volume of waste gas, and engenders a high cost of treatment.
  • deodorization of foul air has been carried out by the method of washing with a detergent, the method of adsorption, the method of direct combustion, the method of catalytic combustion, the method of oxidation with ozone, etc.
  • These methods invariably have both merits and demerits of their own and leave much to be desired.
  • the detergent method yields a large volume of waste water and incurs a large cost for the disposal of waste water.
  • the adsorption method which mostly uses activated carbon as an adsorbent has the disadvantage that devices such as for replacement of activated carbon are difficult to maintain because the adsorbent is liable to catch fire and is quickly deprived of the deodorizing effect.
  • the direct combustion method requires to use fuel and, therefore, entails a high running cost, demands a careful consideration on safety of operation, and suffers a great expense for a voluminous plant.
  • the temperature of the catalyst bed must be maintained in the range of 300° to 450° C.
  • the gas to be treated has a low temperature or the flammable substance is present in a low concentration, therefore, this method suffers from the disadvantage that the running cost is inevitably high.
  • the ozone oxidation method effects elimination of a component of offensive odor by making use of the powerful oxidizing action of ozone.
  • this method effects the treatment at a low temperature in the neighborhood of normal room temperature, it enjoys a low operating cost as compared with the various methods mentioned above Since the reaction of ozone with the component of offensive odor in the gaseous phase proceeds slowly, this method necessitates adoption of a long and voluminous reactor The method further suffers from the disadvantage that the unaltered portion of ozone is released into the atmosphere possibly to induce secondary air pollution.
  • the first method effects deodorization of a foul gas by the use of an apparatus provided with an ozone generator and an ozone decomposition filter (Japanese Patent Laid-Open SHO 61(1986)-29,358.)
  • This method has no possibility of causing secondary air pollution because the unaltered portion of ozone is forcibly decomposed before it is released into the atmosphere. Since both the unaltered portion of ozone and the component of offensive odor are decomposed in the gas phase, the reactor to be used is required to possess a large capacity for the reason mentioned above. If the reactor has a small capacity, there ensues the disadvantage that no sufficient deodorizing effect is obtained because the foul gas under treatment passes the ozone decomposition filter before it is thoroughly deodorized.
  • the second method resides in using a catalyst for the purpose of accelerating the reaction of ozone with the component of offensive odor thereby ensuring thorough oxidation of the component of offensive odor and, at the same time, effecting catalytic decomposition of the unaltered portion of ozone.
  • the carrier is consumed by the combustion of carbon with ozone and the carrier possesses such a large adsorbing capacity as to adsorb the product of oxidation and, as an inevitable result, the catalyst suffers from rapid deterioration and fails to offer an adequate service life.
  • the latter catalyst cannot be expected to offer an adequate service life because sulfur compounds (such as methyl mercaptan and hydrogen sulfide) which are representative ingredients of the component of offensive odor are oxidized into SO 3 and this product of oxidation is deposited cumulatively on the active alumina of the carrier.
  • sulfur compounds such as methyl mercaptan and hydrogen sulfide
  • An object of this invention is to provide a novel method for the purification of a gas and a catalyst to be used therefor.
  • Another object of this invention is to provide for catalytic decomposition of ozone contained in a gas into oxygen, an inexpensive ozone decomposition catalyst having excellent low-temperature activity and ability to remove the offensive odor component of a gas by catalytic oxidative decomposition of the said component with ozone, a method for inexpensive deodorization capable of producing a stable and efficient deodorizing effect over a long period and substantially eliminating release of the unaltered portion of ozone into the atmosphere.
  • a catalyst for the purification of a gas comprising a component A composed of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus.
  • the objects are also accomplished by a catalyst for the purification of a gas, comprising a component A composed of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of the component B is a proportion in the range of not more than 150 parts by weight as oxide, where the element selected is manganese, iron, cobalt, nickel, or silver or in the range of not more than 10 parts by weight as metal where the element is platinum palladium, or rhodium repectively based on 100 parts by weight of the component
  • the objects are also accomplished by passing an ozone-containing gas through a bed of the catalyst.
  • the objects mentioned above are accomplished by setting up a catalyst bed in a path for the flow of the gas and intermittently introducing ozone into the gas flowing through the catalyst bed.
  • the catalyst bed brings about desirable results when, as the catalyst for the bed, there is used a catalyst which comprises a component A composed of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of the component B is a proportion in the range of not more than 150 parts by weight as oxide where the aforementioned element selected is manganese, iron, cobalt, nickel, or silver or in the range of not more than 10 parts by weight as metal where the aforementioned element is platinum, palladium, or rhodium repectively based on 100 parts by weight of the component A as composite oxide.
  • a catalyst which comprises a component A composed of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium
  • the component A in the catalyst may be substituted with an activated carbon.
  • the catalyst of the present invention is such that the oxide of the component A thereof exhibits an outstanding ability to effect ozone decomposition and deodorization at low temperatures not exceeding 60 ° C. and the catalyst obtained by addition of the component B to the component A manifests high activity in the ozone decomposition and the deodorization at extremely low temperatures in the range of -10 to 25° C.
  • the catalyst contemplated by the present invention is characterized by using as a catalytic component thereof a binary composite oxide comprising titanium and silicon (hereinafter referred to as "TiO 2 --SiO 2 "), a binary composite oxide comprising titanium and zirconium (hereinafter referred to as “TiO 2 --ZrO 2 "), a binary composite oxide titanium and phosphorus comprising titanium and phosphorus (hereinafter referred to as “TiO 2 --P 2 O 5 "), a ternary composite oxide comprising titanium, silicon, and zirconium (hereinafter referred to as “TiO --SiO 2 --ZrO 2 "), a ternary composite oxide comprising titanium, silicon, and phosphorus (hereinafter referred to as “TiO 2 --SiO 2 --P2O 5 "), a ternary composite oxide comprising titanium, zirconium, and phosphorus (hereinafter referred to as "TiO 2 --ZrO 2 --P 2 O 5 "), or a
  • the binary composite oxide comprising titanium and silicon as stated in the report of Kozo Tanabe "Catalyst,” Vol. 17, No. 3, page 72 (1975), has been widely known as a solid acid. It exhibits conspicuous acidity not found in either of the component oxides thereof and possesses a large surface area.
  • the TiO 2 --SiO 2 is not a mere mixture of titanium dioxide with silicon dioxide but is a product which is inferred to manifest the peculiar physical attributes mentioned above because titanium and silicon are combined to form the so-called binary type oxide. Further, the TiO 2 --ZrO 2 , TiO 2 --P 2 O 5 , TiO 2 --SiO 2 --ZrO 2 , TiO 2 --SiO 2 --P 2 O 5 , TiO --ZrO 2 --P 2 O 5 , and TiO 2 --SiO 2 --ZrO 2 --P 2 O 5 are characterized as composite oxides possessing the same qualities as TiO 2 --SiO 2 .
  • the composite oxides on analysis by the X-ray diffraction, are found to possess an amorphous or substantially amorphous microstructure.
  • the mechanism which is responsible for the outstanding activity the catalyst of this invention manifests in ozone decomposition and deodorization particularly at low temperatures has not been fully elucidated. It is, however, considered that the various properties of the composite oxides produce desirable effects on their activity in ozone decomposition and deodorization. It is further considered that the composite oxide, by addition thereto of any of such elements as manganese, iron, nickel, cobalt, silver, platinum, palladium, and rhodium or the compounds thereof, are enabled to manifest their activity in ozone decomposition more effectively.
  • TiO 2 --SiO 2 , TiO 2 --ZrO 2 , TiO 2 --P 2 O 5 , TiO --SiO --ZrO 2 , TiO 2 --SiO 2 --P 2 O 5 , TiO 2 --ZrO 2 --P 2 O 5 and TiO 2 --SiO 2 --ZrO 2 --P 2 O 5 one of which is selected to constitute the component A of the catalyst of this invention are desired to have a surface area exceeding 30 m 2 /g, preferably falling in the range of 100 to 250 m 2 /g.
  • the component A of the catalyst brings about better results when it has a percentage composition such that the TiO 2 accounts for a proportion in the range of 20 to 95 mol% and the SiO 2 , ZrO 2 P 2 O 5 , or the sum of SiO 2 and ZrO 2 , that of SiO 2 and P 2 O 5 , that of ZrO 2 and P 2 O 5 , or that of SiO 2 , ZrO 2 , and P 2 O 5 accounts for a proportion in the range of 5 to 80 mol% (invariably based on the sum of TiO 2 + ZrO 2 +SiO 2 +P 2 O 5 taken as 100 mol%), preferably the former oxide accounts for a proportion in the range of 30 to 90 mol% and the latter oxide for a proportion in the range of 10 to 70 mol%.
  • the catalyst of this invention is preferred to have a composition wherein the component B contains at least one element for a proportion in the range of not more than 150 parts by weight, preferably 0 01 to 150 parts by weight, more preferably 10 to 60 parts by weight where the element to be selected is manganese (Mn), silver (Ag), iron (Fe), cobalt (Co), or nickel (Ni) as oxide or in the range of not more than 10 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0 2 to 5 parts by weight where the element is platinum (Pt), palladium (Pd), or rhodium (Rh) as metal, respectively based on 100 parts of the component A as composite oxide. From the point of activity in ozone decomposition and durability of the catalyst, it is preferred to use manganese oxides, more preferably beta-form manganese oxide, or it is preferred to use palladium as the component B.
  • the catalyst component B falls outside the aformentioned range, then the produced catalyst is deficient in oxidative activity. If any of the noble metals such as platinum, palladium, or rhodium is used in an unduly large amount, cost of raw materials is high and the effect to be manifested is not proportionately increased.
  • the titanium source may be selected from among inorganic titanium compounds such as titanium chloride and titanium sulfate and organic titanium compounds such as titanium oxalate and tetraisopropyl titanate and the silicon source from among inorganic silicon compounds such as colloidal silica, water glass, and silicon tetrachloride and organic silicon compounds such as tetraethyl silicate.
  • inorganic titanium compounds such as titanium chloride and titanium sulfate and organic titanium compounds such as titanium oxalate and tetraisopropyl titanate
  • the silicon source from among inorganic silicon compounds such as colloidal silica, water glass, and silicon tetrachloride and organic silicon compounds such as tetraethyl silicate.
  • Some of the raw materials enumerated above may contain a minute amount of extraneous substance.
  • the preparation of the TiO 2 --SiO 2 is attained by any of the following methods.
  • a method which comprises adding an aqueous sodium silicate solution to titanium tetrachloride, causing them components to react with each other and give rise to a precipitate separating and washing the precipitate, drying the washed precipitate, and calcining the dry precipitate at a temperature in the range of 300° to 650° C, preferably 350° to 600° C.
  • a method which comprises adding ethyl silicate (C 2 H 5 O ) 4 Si to a water-alcohol solution of titanium tetrachloride thereby causing hydrolysis and consequent precipitation, separating and washing the resulting precipitate, drying the washed precipitate, and calcining the dry precipitate at a temperature in the range of 300° to 650° C., preferably 350° to 600° C.
  • a method which comprises adding ammonia to a water-soluble solution of titanium oxygen chloride (TiOCl ) and ethyl silicate thereby giving rise to a precipitate, separating and washing the precipitate, drying the washed precipitate, and calcining the dry precipitate at a temperature in the range of 300° to 650° C., preferably 350 to 600° C.
  • TiOCl titanium oxygen chloride
  • the method of (1) proves to be particularly desirable. Specifically, this method is carried out as follows: If the catalyst component B falls outside the aforementioned range, then the produced catalyst is low in oxidative activity in commercial use although it can be used. If any of the noble metals such as platinum, palladium, and rhodium is used in an unduly large amount, the cost of raw material is high and the effect to be manifested is not proportionately increased.
  • Examples of the titanium source and the silicon source are weighed out in amounts to form a composite oxide consisting of TiO 2 and SiO 2 in a predetermined ratio, mixed in the form of an acidic aqueous solution or as a sol containing titanium and silicon in a concentration in the range of 1 to 100 g/liter, preferably 10 to 80g/liter as oxide, and then held at a temperature in the range of 10° to 100° C.
  • the solution or sol is kept stirred and aqueous ammonia added dropwise thereto meanwhile as a neutralizing agent, for a period of 10 minutes to three hours until a coprecipitate composed of titanium and silicon is formed at a pH in the range of 2 to 10.
  • This coprecipitate is separated by filtration, thoroughly washed, then dried at a temperature in the range of 80° to 200° C. for a period of 1 to 10 hours, and calcined at a temperature in the range of 300° to 650° C., preferably 350° to 600° C. for a period of one to 10 hours, preferably 2 to 8 hours, to yield to TiO 2 --SiO 2 .
  • the TiO --ZrO 2 --SiO 2 is prepared by the same method as used for the preparation of the titanium and silicon.
  • the zirconium source may be selected from among inorganic zirconium compounds such as zirconium chloride and zirconium sulfate and organic zirconium compounds such as zirconium oxalate. Specifically, by handling such a zirconium compound together with titanium tetrachloride or oxychloride suitably by the methods described above, the TiO 2 --ZrO 2 --SiO 2 can be easily prepared.
  • the amount of zirconium to be present in this ternary composite oxide is desired to be not more than 30% by weight as ZrO 2 , based on the total amount of the TiO 2 +ZrO 2 +SiO 2
  • the preparation of the TiO 2 --ZrO 2 can be carried out in the same manner as described above.
  • the titanium source may be selected from among inorganic titanium compounds such as titanium chloride and titanium sulfate and organic titanium compounds such as titanium oxalate and tetraisopropyl titanate and the phosphorus source from among phosphorus compounds such as ammonium phosphate, phosphoric acid, and phosphorus pentoxide.
  • inorganic titanium compounds such as titanium chloride and titanium sulfate
  • organic titanium compounds such as titanium oxalate and tetraisopropyl titanate
  • the phosphorus source from among phosphorus compounds such as ammonium phosphate, phosphoric acid, and phosphorus pentoxide.
  • the preparation of the TiO 2 --P 2 O 5 is carried out as follows.
  • Compounds selected severally from the aforementioned groups of typical examples of the titanium source and the phosphorus source are weighted out in amounts to form a composite oxide consisting of titanium and phosphorus in a predetermined ratio, stirred to give a mixture containing titanium and phosphorus in a concentration in the range of 1 to 100 g/liter, preferably 10 to 80 g/liter as oxide, and left aging at a temperature in the range of 10° to 100° C thereby giving rise to a precipitate.
  • the precipitate is separated by filtration, thoroughly washed, then dried at a temperature in the range of 80° to 200° C., for one to 10 hours, and calcined at a temperature in the range of 300° to 800° C., preferably 350° to 600° C., for one to 10 hours, preferably 2 to 8 hours, to yield to TiO 2 --P 2 O 5 .
  • TiO 2 --SiO 2 --P 2 O 5 , TiO 2 --ZrO 2 --P 2 O 5 , and TiO 2 --SiO 2 --ZrO 2 --P 2 O 5 can be prepare by adopting the same method as described above.
  • a final catalyst can be obtained by the following method.
  • the catalyst is obtained by mixing TiO 2 --SiO 2 with a binder for molding such as starch, methyl cellulose, etc., kneading the resulting mixture with a suitable amount of water, molding the resulting blend in the form of pellets or a honeycomb, with an extrusion molder, drying the molded article at a temperature in the range of 50° to 120° C., and thereafter calcining the dry molded article at a temperature in the range of 300° to 800° C., preferably 350° to 600° C., for one to 10 hours, preferably 2 to 6 hours under a current of air.
  • a binder for molding such as starch, methyl cellulose, etc.
  • 5 to 90% by weight, preferably 10 to 60% by weight, of the aforementioned component A may be substituted with activated carbon for the purpose of enabling the catalyst of this invention to substantially improve its activity in deodorization and ozone decomposition to a greater extent.
  • activated carbon For this replacement, commercially available activated carbon can be employed. It may be used in a chemically or physically modified form of the activated carbon.
  • the component A is desired to account for a proportion in the range of 95 to 10% by weight and the activated carbon for a proportion in the range of 5 to 90% by weight.
  • a final deodorant article can be obtained by the following method.
  • the deodorant is produced by thoroughly mixing TiO 2 --SiO 2 powder with activated carbon optionally further with a molding aid, blending the resulting mixture with a suitable amount of water, molding the resulting blend into an article of desired shape, then drying the article, and calcining the dry shaped blend when necessary.
  • activated carbon is generally used in the form of powder, it may be used partly in the form of short fibers.
  • the molding can be effected by any of the various known methods such as compression molding and extrusion molding.
  • the drying of the shaped composite article is effected at a temperature in the range of 50° to 200° C. and the calcining step is desirably carried out in a non-oxidizing atmosphere because the activated carbon is flammable.
  • the flammable substance is present in a low concentration, this calcination may none the less be carried out in the air.
  • the calcination is performed at a temperature in the range of 200° to 600° C., preferably 200° to 400° C., for a period of 1 to 10 hours, preferably 2 to 8 hours. When the calcination is not required, it can be omitted rather advantageously. Though the calcination performed at high temperatures results in improvement of the strength of the shaped composite article, it has the possibility of decreasing the specific surface area of the deodorant and lowering the deodorizing ability thereof.
  • the catalyst of the present invention which comprises the component A and the activated carbon may additionally incorporate therein a carrier such as alumina, silica, etc. or some other known deodorant.
  • the conversion of the component A to a final catalyst by the addition thereto of manganese, iron, nickel, cobalt, silver, platinum, palladium, or rhodium is effected by impregnating the shaped article of component A with an aqueous solution of the salt of the metal, drying and calcining the dry shaped article.
  • this conversion may be accomplished by adding the aqueous solution of metal salt in conjunction with a molding aid to the component A powder, kneading them, and molding the resulting blend.
  • the catalyst of this invention permits additional use of a carrier.
  • a carrier examples of the material usable for the carrier are alumina, silica, silica-alumina, bentonite, diatomaceous earth, silicon carbide, titania, zirconia, magnesia, cordierite, mullite, pumice, activated carbon, and inorganic fibers.
  • the combination of the catalyst with the carrier can be effected, for example, by preparing a slurry comprising the component A and other components of the catalyst and impregnating granular silicon carbide with the slurry thereby depositing the catalyst on the carrier.
  • Other methods available for the production of the catalyst of this invention would be apparent to those skilled in the art.
  • the acceptable shapes of the catalyst article include not only the pellets and the honeycombs mentioned above but also cylinders, tubes, plates, ribbons, corrugated sheets, pipes, doughnuts, lattices, and monolithic shapes.
  • lt is preferred to use the honeycomb form having a nominal diameter of penetration pores in the range of 0.7 to 3mm, wall thickness of cells in the range of 0.2 to 0 5mm, and aperture ratio thereof not less than 50%, preferably in the range of 50 to 80%.
  • the space availability of an ozone decomposition apparatus is also often limited Therefore, the reactor for catalyst is required to be small one.
  • the starting material for the component B which is used in combination with the component A in the catalyst of the present invention can be suitably selected from among oxides, hydroxides, inorganic acid salts, and organic acid salts, particularly ammonium salts, oxalates, nitrates, sulfates, and halogenates. Even when other binary through quaternary composite oxide is used as the component A, the deposition of the component B on a carrier is effected in the same manner as the TiO --SiO 2 composite oxide.
  • the deodorizing catalyst contemplated by the present invention can be used for the treatment of any of various foul gases emanating from food storages, garbage dumps, septic tanks, sewage disposal plants, trash incinerators, cleaning shops, printing shops, painting shops, and chemical plants in general.
  • the component of offensive odor there can be cited hydrogen sulfide, methyl sulfide, methyl mercaptan, methyl disulfide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isobutylamine, pyridine, acetone, methylethyl ketone, butyric acid, acetaldehyde, acrolein, phenol, benzene, xylene, toluene, and butenes. Gases containing these substances can be substantially completely deodorized by the method of this invention.
  • the ozone concentration is roughly in the range of 0.01 to 10,000 ppm, though not critically.
  • the ozone decomposing agent of the present invention can be used for both gases and aqueous solutions containing ozone.
  • the use of this agent is generally accomplished by passing a gas or solution under treatment through a bed packed with the ozone decomposing agent.
  • the space velocity of the gas or solution for this passage generally falls in the range of 1,000 to 100,000 hr -1 , preferably 3,000 to 50,000 hr -1 .
  • the method which uses packed beds of the ozone decomposition agent of this invention and packed beds of the conventional ozone decomposing agent in a multistage system brings about highly desirable results
  • a bed of activated carbon is used for the removal of ozone from a waste gas containing ozone in a high concentration, for example, the operation is hardly feasible because the bed may possibly encounter ignition and explosion and undergo heavy pulverization
  • a bed packed with the ozone decomposing agent of the present invention is set up on the upstream side of the path for the flow of the waste gas under treatment, the system enables the ozone concentration of the waste gas to be lowered in the former bed and permits the remaining ozone in the gas to be further removed in the latter activated carbon catalyst bed.
  • the deodorization of a foul gas by the use of the catalyst of this invention is accomplished by a method which comprises continuously introducing ozone at a prescribed rate into the foul gas containing a component of offensive odor and passing the resulting mixed gas over a bed of the catalyst set up on the downstream side in the path for the flow of the gas under treatment thereby effecting catalytic removal of the component of offensive odor from the gas under treatment.
  • the concentration of the ozone introduced as described above into the foul gas is determined by the attributes and concentration of the component of offensive odor in the gas, other reaction conditions such as, for example, the reaction temperature, the kind of the catalyst, and the amount of the catalyst. This concentration is desired to fall in the range of 0.5 to 1,000 mols, preferably 1 to 10 mols, per mol of the component of offensive odor.
  • the reaction temperature is in the range of -10° to 400° C., preferably 0° to 300° C.
  • the space velocity is in the range of 1,000 to 100,000 hr -1 , preferably 3,000 to 50,000 hr -1 .
  • the deodorization of a foul gas by the present invention may be attained by a method which enables the deodorizing effect to be maintained for a long period by alternately repeating the first step of deodorizing the foul gas by removing the catalyst bed having adsorbed thereon a component of offensive odor from the gas stream and the second step of intermittently introducing ozone into the thus degenerated bed of catalyst thereby decomposing the adsorbate and regenerating the catalyst bed.
  • the salient feature of this method resides in the fact that the introduction of ozone into the foul gas in motion of the purpose of regenerating the degenerated adsorbent can be effected without interrupting the flow of the gas under treatment.
  • the ozone thus introduced fulfills the role of removing the component of offensive odor from the gas under treatment and, at the same time, removing the adsorbate from the catalyst bed by decomposition.
  • the method under discussion does not require operate alternate peration or two columns of adsorbent beds, one for the adsorption and the other for desorption and regeneration. For this method, it suffices to use only one column is needed to effect simultaneous treatments of adsorption and regeneration.
  • the conditions for the adsorption and regeneration are selected, depending on the composition of the gas under treatment and the concentration of the component of offensive odor. They can be found by a simple test.
  • the space velocity of the gas relative to the adsorbent is desirably fixed in the range of 100 to 1000 hr -1 and the concentration of ozone during the introduction thereof for regeneration in the range of 1 to 100 ppm.
  • the ozone concentration is lower than the range just mentioned, the regeneration is obtained with poor efficiency and traces of the foul order are detected.
  • the ozone concentration is higher than the range though the regeneration proceeds quickly, the unaltered portion of ozone passes into the ambient air and can also be readily detected.
  • the intermissions between and the durations of the intermittent introduction of ozone are desired to be each in the range of 30 minutes to 12 hours, per period of roughly one to 24 hours.
  • the intermittent introduction of ozone can be easily effected by programming the pattern of intermission in advance and combining an ozone generator and a timer in accordance with the programmed pattern.
  • a composite oxide comprising titania and silica was prepared as follows.
  • An aqueous sulfuric acid solution of titanyl sulfate having the following composition was used as a titanium source.
  • aqueous ammonia (NH 3 , 25% ) were added to 40 liters of water and 2.4 kg of Snowtex-NCS-30 (silica sol containing about 30% by weight of silica as SiO 2 ; product of Nissan Chemicals Industries Ltd.) were added further added thereto.
  • Snowtex-NCS-30 sica sol containing about 30% by weight of silica as SiO 2 ; product of Nissan Chemicals Industries Ltd.
  • a dilute titanium-containing aqueous sulfuric acid solution prepared by diluting 15.3 liters of the above aqueous sulfuric acid solution of titanyl sulfate with 30 liters of water was gradually added dropwise while under agitation to give rise to a coprecipitate gel.
  • the resulting reaction mixture was left standing for 15 hours.
  • the TiO 2 --SiO 2 gel thus obtained was separated by filtration, washed with water, and then dried at 200° C. for 10 hours.
  • the dry TiO 2 --SiO 2 gel was calcined under an atmosphere of air at 550° C. for six hours.
  • the powder which will be referred to hereinafter as TS-1 was used to prepare an ozone decomposition catalyst as follows.
  • a kneader In a kneader, 1.0 kg of the TS-1 powder was thoroughly mixed with 20 g of microcrystalline cellulose (produced by Asahi Chemical Industry Co., Ltd. and marketed under trademark designation of "Avicel") and a suitable amount of water. The resulting mixture was molded in the form of pellets 3.0 mm in diameter and 3.0 mm in length with an extrusion molding machine. The pellets were dried at 100° C. for 10 hours and then calcined under an atmosphere of air at 500° C. for six hours. Consequently, there was obtained a catalyst of formed TiO 2 --SiO 2 .
  • TiO 2 --ZrO 2 was prepared as follows.
  • the TiO 2 --ZrO 2 gel thus obtained was separated by filtration, washed with cold water, and then dried at 200° C for 10 hours. Then, the dry gel was calcined under an atmosphere of air at 550° C. for six hours.
  • the powder thus obtained will be referred to hereinafter as TZ-1.
  • TiO 2 --SiO 2 --ZrO 2 by following the procedures of Examples 1,1A and 2.
  • the powder thus obtained will be referred to hereinafter as TSZ-1.
  • Catalysts formed of TiO 2 --SiO 2 were prepared by following the procedure of Example 1, except that the molar ratio of TiO 2 / /SiO 2 was varied.
  • compositions and BET surface areas of the catalysts thus obtained were as shown in Table 1.
  • a TiO 2 powder was prepared by following the procedure of Example 1, except that use of silica sol was omitted.
  • the TiO 2 powder thus obtained had a BET surface area of 60 m 2 /g.
  • a catalyst formed solely of TiO 2 By using this powder and following the procedure of Example 1A, there was obtained a catalyst formed solely of TiO 2 .
  • a powder solely of SiO 2 containing no titanium was prepared by following the procedure of Example 1
  • the powder thus obtained had a surface area of 250 m 2 /g
  • a catalyst formed solely of SiO 2 By using this powder and following the procedure of Example 1 A, there was obtained a catalyst formed solely of SiO 2 .
  • the mixed powder consequently obtained had a BET surface area of 90 m 2 /g.
  • a catalyst formed of the mixed powder By following the procedure of Example 1A, there was obtained a catalyst formed of the mixed powder.
  • Catalysts were prepared by using the same TS-1 powder as used in Example 1 and following the procedure of Example 8, except that the component for addition to the component A was varied.
  • catalyst sources nitrates of iron, cobalt, nickel, and silver respectively were used.
  • the catalysts were tested for ozone decomposition capactiy by following the procedure of Example 7.
  • the catalyst compositions and the results of the test were as shown in Table 3.
  • Catalysts were prepared by following the procedure of Example 13, excepting palladium and rhodium respectively were used in the place of platinum.
  • the catalysts of this invention provide highly efficient decomposition of ozone at low temperatures not exceeding 50° C., particularly at temperatures approximating to normal room temperature.
  • a composite oxide comprising titanium and phosphorus was prepared as follows.
  • An aqueous sulfuric acid solution of titanyl sulfate having the following composition was used as a titanium source.
  • a titanium-containing aqueous sulfuric acid solution prepared by diluting 10 liters of the above aqueous sulfuric acid solution of titanyl sulfate with 50 liters of cold water was kept at 40° C. and, while under thorough agitation, 40 liters of an aqueous solution containing 4.13 kg of diammonium hydrogen phosphate were gradually added dropwise thereto, to give rise to a precipitate.
  • the resulting reaction mixture was left standing at rest at 80° C. for six hours.
  • the TiO 2 --P 2 O 5 gel consequently obtained was separated by filtration, washed with cold water, and then dried at 150° C. for 10 hours.
  • TPI ozone decomposition catalyst
  • Catalysts formed of TiO 2 --P 2 O 5 were prepared by following the procedure of Example 1, TMexcept that the molar ratio of TiO 2 --P 2 O 5 was varied.
  • compositions and the BET surface areas of the catalysts obtained were as shown in Table 4.
  • Catalysts were prepared by using the same TP-1 powder as used in Example 16 and following the procedure of Example 21, excepting the component for addition to the component A was varied.
  • catalyst sources nitrates of iron, cobalt, nickel, and silver respectively were used.
  • the catalysts were tested for ozone decomposition capacity by following the procedure of Example 20.
  • the catalyst compositions and the results of the test were as shown in Table 6.
  • 500 cc of the catalyst (pellets 3 mm in diameter and 3 mm in length) formed of TiO 2 --P 2 O 5 obtained in Example 16 and 140 ml of an aqueous platinum nitrate solution containing 3.5 g of platinum (Pt) were thoroughly mixed in an evaporation dish to effect impregnation of the catalyst with the solution. Over a water bath, the impregnated catalyst was concentrated and then dried at 120° C. for five hours. Then, the dry impregnated catalyst was calcined under an atmosphere of air at 400° C. for three hours.
  • This catalyst was tested for ozone decomposition capacity by following the procedure of Example 20. The results were as shown in Table 6.
  • Catalysts were prepared by following the procedure of Example 26, except that palladium and rhodium were respectively used in the place of platinum.
  • the catalysts were tested for ozone decomposition capacity by following the procedure of Example 20.
  • the catalyst compositions and the results of the test were as shown in Table 6. It is noted from the data of Tables 5 and 6 that the catalysts of the present invention provide highly efficient decomposition of ozone at low temperatures not exceeding 60° C., particularly at low temperature approximating to normal room temperature.
  • a kneader 10 kg of the TS-1 powder obtained in Example 1 and a suitable amount of water added thereto were thoroughly mixed. The resulting mixture was thoroughly blended in a blender. The homogeneous mixture thus obtained was molded in the form of lattice-shaped honeycombs having visible dimensions of 50 mm in length, 50 mm in width, and mm in length (0.3 mm in wall thickness and 1.4 mm in mesh) with an extrusion molder. The honeycombs were dried at ° C. for five hours and then calcined under an atmosphere of air at 300° C. for two hours. Consequently, there was obtained a deodorizing catalyst formed of TS-lH.
  • a catalyst formed of TZ-1H was prepared by using the TZ-1 obtained in Example 2 and following the procedure of Example 29.
  • a catalyst formed of TSZ-1H was prepared by using the TSZ-1 obtained in Example 3 and following the procedure of Example 29.
  • Catalysts formed of TiO 2 --SiO 2 were prepared by following the procedure of Example 29, excepting the molar ratio of TiO 2 /SiO 2 varied.
  • the compositions and the BET surface areas of the catalysts thus obtained were as shown in Table 7.
  • Ozone was introduced in a concentration of 20 ppm to the inlet side of the catalyst bed, with the reaction temperature at 5° C. After 500 hours' use of the catalyst bed required for stabilization of the catalyst activity, the catalyst was tested for deodorization ratio The results were as shown in Table 8.
  • This catalyst was tested for deodorization capacity by following the procedure of Example 35. The results were as shown in Table 9. The ozone concentration in the outlet gas was less than 0.1 ppm.
  • Catalysts were prepared by following the procedure of Example 36, excepting the component for addition to the component A was varied.
  • Nitrates of iron, cobalt, nickel, silver, and platinum, and chlorides of palladium and rhodium were used as catalyst sources.
  • the catalysts were tested for deodorization capacity by following the procedure of Example 35.
  • the compositions of the catalysts and the results of the test were as shown in Table 9.
  • the ozone concentrations in the outlet gases were invariably less than 0.1 ppm.
  • Catalysts were prepared by following the procedure of Example 36, excepting lattice-like honeycombs of activated alumina and lattice-like honeycombs of activated carbon were used in the place of TS-1H.
  • the catalysts were tested for deodorization capacity by following the procedure of Example 35.
  • the compositions of the catalysts and the results of the test were as shown in Table 9.
  • the catalysts of the present invention permit deodorization to be effected with high efficiency at such a low temperature as 5° C.
  • a kneader 750 g of the TS-1 powder obtained in Example 1 and 250 g of a commercially available activated carbon were thoroughly mixed, with a suitable amount of water added thereto. The resulting mixture was thoroughly blended in a blender. The homogeneous mixture thus obtained was molded in the form of pellets 5.0 mm in diameter and 6.0 mm in length with an extrusion molder. The pellets were dried at 150° C. for two hours. Consequently there was obtained an ozone decomposing agent formed of TiO 2 --SiO 2 --C.
  • An ozone decomposing agent formed of TiO 2 --ZrO 2 --C was prepared by using the TZ-1 obtained in Example 2 and following the procedure of Example 44.
  • An ozone decomposing agent formed of TiO 2 --SiO 2 ZrO 2 --C was prepared by using the TSZ-1 obtained in Example 3 and following the procedure of Example 44.
  • Ozone decomposing agents formed of TiO 2 --SiO 2 --C were prepared by following the procedure of Example 44, except that the weight ratio of TiO 2 --SiO 2 to the activated carbon was varied.
  • the compositions of the ozone decomposing agents thus obtained were as shown in Table 10.
  • An ozone decomposing agent formed solely of activated carbon was prepared by following the procedure of Example 44, except that granular activated carbon was used in the place of the TS-1 powder.
  • a deodorant formed of TiO 2 --ZrO 2 --C was prepared by using the TZ-1 obtained in Example 2 and following the procedure of Example 51.
  • a deodorant formed of TiO 2 --SiO 2 --ZrO 2 --C was prepared by using the TSZ-1 obtained in Example 3 and following the procedure of Example 51.
  • Deodorants formed of TiO 2 --SiO 2 --C were prepared by following the procedure of Example 51, excepting the weight ratio of the TiO 2 --SiO 2 and the activated carbon was varied. The compositions of the deodorants consequently obtained were as shown in Table 12.
  • a deodorant formed solely of activated carbon was prepared by following the procedure of Example 51, except that powdered activated carbon was used in the place of the TS-1 powder.
  • Example 51-56 and Control 7 were tested for capacity for deodorization of a foul gas as follows.
  • a deodorant was placed in a container having an inner volume of 2 liters. Air (20° C.) containing 300 ppm of ammonia or hydrogen sulfide was introduced to the deodorant.
  • the deodorant covered with the air was left standing at rest. At intervals of 30 minutes, 60 minutes, and 90 minutes, the air was tested for residual ammonia or hydrogen sulfide concentration to determine deodorization ratio.
  • the results of the test were as shown in Table 13.
  • a tube made of Pyrex glass was packed with the lattice-like honeycombs of catalyst TS-1H obtained in Example 29 so as to preclude the incoming gas from finding a short path.
  • Air containing 5 ppm of trimethylamine as a typical component of offensive odor was continuously introduced at a flow rate of 2.5 Nm 3 /hr to the catalyst bed at 25° C.
  • the gas at the outlet of the catalyst bed was analyzed to determine trimethylamine concentration. Then the flow of the gas was continued. After the catalyst bed was exhausted and the concentration of the component of offensive odor in the gas at the outlet of the catalyst bed roughly equalled the concentration at the inlet, introduction of ozone to the tube interior was started.
  • the introduction of ozone was adjusted so that the ozone concentration in the gas would remain at 30 ppm.
  • the ozone introduction was continued for five hours.
  • the gas at the outlet of the catalyst bed was analyzed for ozone and trimethylamine contents.
  • the ozone introduction was discontinued and the introduction of the gas containing the component of offensive odor was continued to effect degeneration of the catalyst bed for 10 hours.
  • the 9as at the outlet of the catalyst bed was analyzed.
  • the same operation of intermittently introducing ozone to the exhausted catalyst bed as described above was repeated a total of 10 times After elapse of 10 hours, the gas at the outlet of the Catalyst bed was analyzed.
  • Example 59 The catalyst obtained in Example 59 was subjected to the procedure of Example 59, except that the temperature of the catalyst bed was kept at 0° C.
  • Example 30 The catalyst of TZ-1H obtained in Example 30 was tested for adsorption and regeneration by following the procedure of Examples 59 and 60. The results were as shown in Tables 15 and 16.
  • Example 31 The catalyst of TSZ-1H obtained in Example 31 was tested for adsorption and regeneration by following the procedure of Examples 59 and 60. The results were as shown in Tables 15 and 16.
  • This catalyst was tested for adsorption and regeneration by following the procedure of Example 60, excepting the concentration of the introduced ozone was fixed at 20 ppm and the duration of the introduction was two hours. The results of the test were as shown in Table 17.
  • Example 63 The catalyst obtained in Example 63 was tested for adsorption and regeneration by following the procedure of Example 63, excepting the catalyst bed temperature was fixed at 25° C. The results were as shown in Table 18.
  • Adsorbents were prepared by following the procedure of Example 63, excepting the component B for addition to the component A was varied.
  • nitrates of iron, cobalt, nickel, silver, and platinum and chlorides of palladium and rohdium were used.
  • the catalysts thus obtained were tested for adsorption and regeneration by following the procedure of Example 63
  • the catalyst compositions and the results of the test were as shown in Table 17.
  • Example 65-71 The catalysts obtained in Examples 65-71 were tested for adsorption and regeneration by following the procedure of Example 64 The catalyst compositions and the results of the test were as shown in Table 18.
  • Catalyst were prepared by following the procedure of Example 63, except that lattice-like honeycombs of activated alumina and lattice-like honeycombs of activated carbon were used in the place of the TS-1H.
  • the catalysts were tested for adsorption and regeneration by following the procedure of Example 64.
  • the catalyst compositions and the results of the test were as shown in Table 18.
  • the catalysts prepared in Examples 79-82 were tested for the activity of ozone decomposition by following the procedure of Example 20.
  • the reaction temperature was at 2° C.
  • the results were as shown in Table 19.
  • Example 79-82 The catalysts prepared in Example 79-82 were tested for deodorizing activity by following procedure of Example 35, excepting 10.5 ml of pellets of catalysts were packed in a reaction tube made of Pyrex glass having an inner diameter of 20 mm, and steam saturated air containing ppm of trimethylamine and methyl mercaptan was introduced to the catalyst bed at a flow rate of 0.21 Nm 3 /hr (space velocity of 20,000 hr -1 )at a reaction temperature of 2° C. The results obtained were as shown in Table 20.
  • the catalysts obtained in Examples 36, 42 and Control 4 were tested for durability as follows: In a reaction tube made of Pyrex glass, 250 cc of lattice-like honeycombs of catalyst were packed. Air containing 40% of relative humidity, and containing 5 ppm of ozone was introduced to the catalyst bed at a flow rate of 12.5Nm 3 /hr (space velocity 50,000hr-1) at room temperature. Change of ozone decomposition ratio with time was tested for days. The results were shown in Table 21.
  • a composite oxide comprising titania and silica was prepared as follows.
  • An aqueous sulfuric acid solution of titanyl sulfate having the following composition was used as a titanium source.
  • the dry TiO 2 --SiO 2 gel was calcined under an atmosphere of air at 550° C. for six hours.
  • the powder thus obtained was used to prepare deodorant formed of lattice-like honeycomb.
  • honeycomb obtained had penetration pores 1 4mm in individual diameter of wall thickness of cells of 0.33 mm and the aperture ratio of this honeycomb was 64%
  • Catalysts formed of lattice-like honeycombs were prepared by using the same composition as used in Example 93 and following the procedure of Example 93, excepting the form of catalysts were varied
  • Ozone was introduced in a concentration of 20 ppm to the inlet side of the catalyst bed, with the reaction temperature at 5° C. After 500 hours' use of the catalyst bed required for stabilization of the catalyst activity, the catalyst was tested for deodorization ratio. The losses of pressure were tested at above-mentioned operating condition. The results were as shown in Table 22.

Abstract

A catalyst for the purification of a gas containing ozone or a component of offensive odor is composed of (A) a composite oxide comprising (a) titanium and (b) at least one element selected from the group consisting of Si, Zr, and P and (B) at least one element selected from the group consisting of Mn, Fe, Co, Ni, Ag, Pt, Pd, and Rh.

Description

This application is a continuation of application Ser. No. 07/549,828, filed Aug. 9, 1990, now abandoned, which is a continuation-in-part of 181,499, filed Apr. 14, 1988, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for the purification of a gas and a catalyst for use in the purification. More particularly, it relates to a method for catalytically decomposing ozone contained in a gas or catalytically decomposing a component of offensive odor in a gas through oxidation with ozone and to a catalyst used for the decomposition.
2. Description of the Prior Art
Ozone possesses a strong oxidizing ability and, on decomposition, converts itself into harmless oxygen. Thus, it has found extensive utility in various applications aimed at deodorizing, sterilizing, and bleaching various substances and even lowering the COD level of plant effluents. Unfortunately, since part of the ozone so used in varying treatments is released in its unaltered form into the air, the stray ozone has the possibility of giving rise to secondary environmental pollution such as, for example, generation of a photochemical smog. In the case of an airplane in flight through the stratosphere, since the air containing ozone is drawn into the interior of the airplane, the passengers and the crew aboard the airplane may possibly be exposed to the adverse effect of the ozone in the air.
Further, the issue of ozone from machines incorporating therein various high voltage generating devices such as, for example, xerographic copying machines has recently been posing a problem. Since these machines are installed mainly in rooms, the ozone so generated pollutes the interiors of the rooms, though the amount of the ozone so generated is very small.
The odor of ozone can be perceived even when the ozone is present in a concentration of not more than 1 ppm. When ozone is present in the air in a concentration exceeding 2 ppm, it stimulates the respiratory system of a person inhaling the air and does harm to the person's body. The air which contains the ozone issuing from a varying ozone sources must be detoxified by removal of the ozone.
As conventional techniques used for disposal of spent ozone, the method using activated carbon, the method using a liquid detergent, and the method resorting to thermal decomposition have been available When the activated carbon method is utilized for the treatment of air containing ozone in a low concentration, the activated carbon must be replenished as it is consumed in consequence of progress of the decomposition of ozone. When this method is used for the treatment of air containing ozone in a high concentration, the activated carbon must be handled attentively because it has the possibility of being ignited and burnt by the heat of reaction.
The liquid detergent method resides in purifying air containing spent ozone with the aqueous solution of a reducing substance. Thus, the treatment costs much and gives rise to a problem of waste water disposal.
The thermal decomposition method has the disadvantage that it requires application of heat to a temperature of not less than 300° C. for the purpose of enhancing the efficiency of decomposition, necessitates an expensive application of heat for the disposal of a large volume of waste gas, and engenders a high cost of treatment.
In recent years, as one approach to the disposal of spent ozone, the method which resorts to catalytic decomposition has been the subject of research. It is held that this method constitutes an advantageous way of removing ozone by decomposition at a low cost because it has no possibility of inducing ignition or explosion and obviates the necessity for waste water disposal.
Regarding the decomposition of ozone, a catalyst using the oxides of nickel, manganese, cobalt, etc. is disclosed as exhibiting an outstanding ability to effect efficient decomposition of ozone in the specification of Japanese Patent Laid-Open SHO 60(1985)-97,049. For practical reasons, however, the necessity for developing a catalyst exhibiting high activity in the range of much lower temperatures has been finding growing recognition.
In recent years, the pollution of air with offensive odor has arisen as a serious social problem and thus the need for development and adoption of new techniques for combatting such odors.
Heretofore, deodorization of foul air has been carried out by the method of washing with a detergent, the method of adsorption, the method of direct combustion, the method of catalytic combustion, the method of oxidation with ozone, etc. These methods invariably have both merits and demerits of their own and leave much to be desired. The detergent method yields a large volume of waste water and incurs a large cost for the disposal of waste water. The adsorption method which mostly uses activated carbon as an adsorbent has the disadvantage that devices such as for replacement of activated carbon are difficult to maintain because the adsorbent is liable to catch fire and is quickly deprived of the deodorizing effect. The direct combustion method requires to use fuel and, therefore, entails a high running cost, demands a careful consideration on safety of operation, and suffers a great expense for a voluminous plant. In the case of the catalytic combustion method, though the plant can be maintained relatively easily, the temperature of the catalyst bed must be maintained in the range of 300° to 450° C. When the gas to be treated has a low temperature or the flammable substance is present in a low concentration, therefore, this method suffers from the disadvantage that the running cost is inevitably high. The ozone oxidation method effects elimination of a component of offensive odor by making use of the powerful oxidizing action of ozone. Since this method effects the treatment at a low temperature in the neighborhood of normal room temperature, it enjoys a low operating cost as compared with the various methods mentioned above Since the reaction of ozone with the component of offensive odor in the gaseous phase proceeds slowly, this method necessitates adoption of a long and voluminous reactor The method further suffers from the disadvantage that the unaltered portion of ozone is released into the atmosphere possibly to induce secondary air pollution.
Two new methods have been proposed as means of overcoming the aforementioned drawbacks of the various conventional methods The first method effects deodorization of a foul gas by the use of an apparatus provided with an ozone generator and an ozone decomposition filter (Japanese Patent Laid-Open SHO 61(1986)-29,358.)
This method has no possibility of causing secondary air pollution because the unaltered portion of ozone is forcibly decomposed before it is released into the atmosphere. Since both the unaltered portion of ozone and the component of offensive odor are decomposed in the gas phase, the reactor to be used is required to possess a large capacity for the reason mentioned above. If the reactor has a small capacity, there ensues the disadvantage that no sufficient deodorizing effect is obtained because the foul gas under treatment passes the ozone decomposition filter before it is thoroughly deodorized.
The second method resides in using a catalyst for the purpose of accelerating the reaction of ozone with the component of offensive odor thereby ensuring thorough oxidation of the component of offensive odor and, at the same time, effecting catalytic decomposition of the unaltered portion of ozone.
As catalysts available for this method, a catalyst having a metal oxide deposited on a carrier made of a carbonaceous material (Japanese Patent Laid-Open SHO 54(1979)-119,371) and a catalyst having a metal oxide deposited on a carrier of activated alumina (Japanese Patent Laid-Open SHO 53(1978)-30,978) have been disclosed.
In the case of the former catalyst, the carrier is consumed by the combustion of carbon with ozone and the carrier possesses such a large adsorbing capacity as to adsorb the product of oxidation and, as an inevitable result, the catalyst suffers from rapid deterioration and fails to offer an adequate service life.
The latter catalyst cannot be expected to offer an adequate service life because sulfur compounds (such as methyl mercaptan and hydrogen sulfide) which are representative ingredients of the component of offensive odor are oxidized into SO3 and this product of oxidation is deposited cumulatively on the active alumina of the carrier.
As described in detail above, with the conventional methods, it is difficult to attain deodorization to a thorough extent and effect substantial elimination of the leakage of the unaltered ozone into the atmosphere.
An object of this invention, therefore, is to provide a novel method for the purification of a gas and a catalyst to be used therefor.
Another object of this invention is to provide for catalytic decomposition of ozone contained in a gas into oxygen, an inexpensive ozone decomposition catalyst having excellent low-temperature activity and ability to remove the offensive odor component of a gas by catalytic oxidative decomposition of the said component with ozone, a method for inexpensive deodorization capable of producing a stable and efficient deodorizing effect over a long period and substantially eliminating release of the unaltered portion of ozone into the atmosphere.
SUMMARY OF THE INVENTION
There is provided a catalyst for the purification of a gas, comprising a component A composed of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus. The objects are also accomplished by a catalyst for the purification of a gas, comprising a component A composed of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of the component B is a proportion in the range of not more than 150 parts by weight as oxide, where the element selected is manganese, iron, cobalt, nickel, or silver or in the range of not more than 10 parts by weight as metal where the element is platinum palladium, or rhodium repectively based on 100 parts by weight of the component A as oxide.
The objects are also accomplished by passing an ozone-containing gas through a bed of the catalyst.
These objects are further accomplished by continuously adding ozone to a gas containing a component of offensive odor and passing the resulting mixed gas through a bed of the catalyst.
In the removal of a component of offensive odor from a gas containing the offensive odor component by introduction of ozone into the gas and consequent decomposition of the offensive odor component, the objects mentioned above are accomplished by setting up a catalyst bed in a path for the flow of the gas and intermittently introducing ozone into the gas flowing through the catalyst bed.
In accordance with this invention, the catalyst bed brings about desirable results when, as the catalyst for the bed, there is used a catalyst which comprises a component A composed of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of the component B is a proportion in the range of not more than 150 parts by weight as oxide where the aforementioned element selected is manganese, iron, cobalt, nickel, or silver or in the range of not more than 10 parts by weight as metal where the aforementioned element is platinum, palladium, or rhodium repectively based on 100 parts by weight of the component A as composite oxide.
Alternatively, 5 to 90% by weight of the component A in the catalyst may be substituted with an activated carbon.
The catalyst of the present invention is such that the oxide of the component A thereof exhibits an outstanding ability to effect ozone decomposition and deodorization at low temperatures not exceeding 60 ° C. and the catalyst obtained by addition of the component B to the component A manifests high activity in the ozone decomposition and the deodorization at extremely low temperatures in the range of -10 to 25° C.
DESCRIPTION OF PREFERRED EMBODIMENT
The catalyst contemplated by the present invention is characterized by using as a catalytic component thereof a binary composite oxide comprising titanium and silicon (hereinafter referred to as "TiO2 --SiO2 "), a binary composite oxide comprising titanium and zirconium (hereinafter referred to as "TiO2 --ZrO2 "), a binary composite oxide titanium and phosphorus comprising titanium and phosphorus (hereinafter referred to as "TiO2 --P2 O5 "), a ternary composite oxide comprising titanium, silicon, and zirconium (hereinafter referred to as "TiO --SiO2 --ZrO2 "), a ternary composite oxide comprising titanium, silicon, and phosphorus (hereinafter referred to as "TiO2 --SiO2 --P2O5 "), a ternary composite oxide comprising titanium, zirconium, and phosphorus (hereinafter referred to as "TiO2 --ZrO2 --P2 O5 "), or a quaternary composite oxide comprising titanium, silicon, zirconium, and phosphorus (hereinafter referred to as "TiO2 --SiO2 --ZrO2 --P2 O5 ")(component A).
Generally, the binary composite oxide comprising titanium and silicon, as stated in the report of Kozo Tanabe "Catalyst," Vol. 17, No. 3, page 72 (1975), has been widely known as a solid acid. It exhibits conspicuous acidity not found in either of the component oxides thereof and possesses a large surface area.
The TiO2 --SiO2 is not a mere mixture of titanium dioxide with silicon dioxide but is a product which is inferred to manifest the peculiar physical attributes mentioned above because titanium and silicon are combined to form the so-called binary type oxide. Further, the TiO2 --ZrO2, TiO2 --P2 O5, TiO2 --SiO2 --ZrO2, TiO2 --SiO2 --P2 O5, TiO --ZrO2 --P2 O5, and TiO2 --SiO2 --ZrO2 --P2 O5 are characterized as composite oxides possessing the same qualities as TiO2 --SiO2.
The composite oxides, on analysis by the X-ray diffraction, are found to possess an amorphous or substantially amorphous microstructure.
The mechanism which is responsible for the outstanding activity the catalyst of this invention manifests in ozone decomposition and deodorization particularly at low temperatures has not been fully elucidated. It is, however, considered that the various properties of the composite oxides produce desirable effects on their activity in ozone decomposition and deodorization. It is further considered that the composite oxide, by addition thereto of any of such elements as manganese, iron, nickel, cobalt, silver, platinum, palladium, and rhodium or the compounds thereof, are enabled to manifest their activity in ozone decomposition more effectively.
The TiO2 --SiO2, TiO2 --ZrO2, TiO2 --P2 O5, TiO --SiO --ZrO2, TiO2 --SiO2 --P2 O5, TiO2 --ZrO2 --P2 O5 and TiO2 --SiO2 --ZrO2 --P2 O5 one of which is selected to constitute the component A of the catalyst of this invention are desired to have a surface area exceeding 30 m2 /g, preferably falling in the range of 100 to 250 m2 /g.
The component A of the catalyst brings about better results when it has a percentage composition such that the TiO2 accounts for a proportion in the range of 20 to 95 mol% and the SiO2, ZrO2 P2 O5, or the sum of SiO2 and ZrO2, that of SiO2 and P2 O5, that of ZrO2 and P2 O5, or that of SiO2, ZrO2, and P2 O5 accounts for a proportion in the range of 5 to 80 mol% (invariably based on the sum of TiO2 + ZrO2 +SiO2 +P2 O5 taken as 100 mol%), preferably the former oxide accounts for a proportion in the range of 30 to 90 mol% and the latter oxide for a proportion in the range of 10 to 70 mol%.
The catalyst of this invention is preferred to have a composition wherein the component B contains at least one element for a proportion in the range of not more than 150 parts by weight, preferably 0 01 to 150 parts by weight, more preferably 10 to 60 parts by weight where the element to be selected is manganese (Mn), silver (Ag), iron (Fe), cobalt (Co), or nickel (Ni) as oxide or in the range of not more than 10 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0 2 to 5 parts by weight where the element is platinum (Pt), palladium (Pd), or rhodium (Rh) as metal, respectively based on 100 parts of the component A as composite oxide. From the point of activity in ozone decomposition and durability of the catalyst, it is preferred to use manganese oxides, more preferably beta-form manganese oxide, or it is preferred to use palladium as the component B.
If the catalyst component B falls outside the aformentioned range, then the produced catalyst is deficient in oxidative activity. If any of the noble metals such as platinum, palladium, or rhodium is used in an unduly large amount, cost of raw materials is high and the effect to be manifested is not proportionately increased.
In the preparation of the TiO2 --SiO2 for use in the present invention, the titanium source may be selected from among inorganic titanium compounds such as titanium chloride and titanium sulfate and organic titanium compounds such as titanium oxalate and tetraisopropyl titanate and the silicon source from among inorganic silicon compounds such as colloidal silica, water glass, and silicon tetrachloride and organic silicon compounds such as tetraethyl silicate. Some of the raw materials enumerated above may contain a minute amount of extraneous substance. Preferably, the preparation of the TiO2 --SiO2 is attained by any of the following methods.
1) A method which comprises mixing titanium tetrachloride with silica sol, adding ammonia to the resulting mixture thereby inducing precipitation, separating and washing the resulting precipitate, drying the washed precipitate, and calcining the dry precipitate at a temperature in the range of 300° to 650° C., preferably 350° to 600° C.
2) A method which comprises adding an aqueous sodium silicate solution to titanium tetrachloride, causing them components to react with each other and give rise to a precipitate separating and washing the precipitate, drying the washed precipitate, and calcining the dry precipitate at a temperature in the range of 300° to 650° C, preferably 350° to 600° C.
3) A method which comprises adding ethyl silicate (C2 H5 O )4 Si to a water-alcohol solution of titanium tetrachloride thereby causing hydrolysis and consequent precipitation, separating and washing the resulting precipitate, drying the washed precipitate, and calcining the dry precipitate at a temperature in the range of 300° to 650° C., preferably 350° to 600° C.
4) A method which comprises adding ammonia to a water-soluble solution of titanium oxygen chloride (TiOCl ) and ethyl silicate thereby giving rise to a precipitate, separating and washing the precipitate, drying the washed precipitate, and calcining the dry precipitate at a temperature in the range of 300° to 650° C., preferably 350 to 600° C.
Among in the preferred methods cited above, the method of (1) proves to be particularly desirable. Specifically, this method is carried out as follows: If the catalyst component B falls outside the aforementioned range, then the produced catalyst is low in oxidative activity in commercial use although it can be used. If any of the noble metals such as platinum, palladium, and rhodium is used in an unduly large amount, the cost of raw material is high and the effect to be manifested is not proportionately increased. Examples of the titanium source and the silicon source are weighed out in amounts to form a composite oxide consisting of TiO2 and SiO2 in a predetermined ratio, mixed in the form of an acidic aqueous solution or as a sol containing titanium and silicon in a concentration in the range of 1 to 100 g/liter, preferably 10 to 80g/liter as oxide, and then held at a temperature in the range of 10° to 100° C. The solution or sol is kept stirred and aqueous ammonia added dropwise thereto meanwhile as a neutralizing agent, for a period of 10 minutes to three hours until a coprecipitate composed of titanium and silicon is formed at a pH in the range of 2 to 10. This coprecipitate is separated by filtration, thoroughly washed, then dried at a temperature in the range of 80° to 200° C. for a period of 1 to 10 hours, and calcined at a temperature in the range of 300° to 650° C., preferably 350° to 600° C. for a period of one to 10 hours, preferably 2 to 8 hours, to yield to TiO2 --SiO2.
The TiO --ZrO2 --SiO2 is prepared by the same method as used for the preparation of the titanium and silicon. In this case, the zirconium source may be selected from among inorganic zirconium compounds such as zirconium chloride and zirconium sulfate and organic zirconium compounds such as zirconium oxalate. Specifically, by handling such a zirconium compound together with titanium tetrachloride or oxychloride suitably by the methods described above, the TiO2 --ZrO2 --SiO2 can be easily prepared. The amount of zirconium to be present in this ternary composite oxide is desired to be not more than 30% by weight as ZrO2, based on the total amount of the TiO2 +ZrO2 +SiO2 The preparation of the TiO2 --ZrO2 can be carried out in the same manner as described above.
For the preparation of the TiO2 --P2 O5, the titanium source may be selected from among inorganic titanium compounds such as titanium chloride and titanium sulfate and organic titanium compounds such as titanium oxalate and tetraisopropyl titanate and the phosphorus source from among phosphorus compounds such as ammonium phosphate, phosphoric acid, and phosphorus pentoxide.
Desirably, the preparation of the TiO2 --P2 O5 is carried out as follows.
Compounds selected severally from the aforementioned groups of typical examples of the titanium source and the phosphorus source are weighted out in amounts to form a composite oxide consisting of titanium and phosphorus in a predetermined ratio, stirred to give a mixture containing titanium and phosphorus in a concentration in the range of 1 to 100 g/liter, preferably 10 to 80 g/liter as oxide, and left aging at a temperature in the range of 10° to 100° C thereby giving rise to a precipitate. The precipitate is separated by filtration, thoroughly washed, then dried at a temperature in the range of 80° to 200° C., for one to 10 hours, and calcined at a temperature in the range of 300° to 800° C., preferably 350° to 600° C., for one to 10 hours, preferably 2 to 8 hours, to yield to TiO2 --P2 O5.
The TiO2 --SiO2 --P2 O5, TiO2 --ZrO2 --P2 O5, and TiO2 --SiO2 --ZrO2 --P2 O5 can be prepare by adopting the same method as described above.
From the TiO2 --SiO2, TiO2 --ZrO2, TiO2 --P2 O5, TiO2 --SiO2 --ZrO2, TiO2 --SiO2 --P2 O5, TiO2 --ZrO2 --P2 O5, or TiO2 --SiO2 --ZrO2 --P2 O5, a final catalyst can be obtained by the following method. For example, the catalyst is obtained by mixing TiO2 --SiO2 with a binder for molding such as starch, methyl cellulose, etc., kneading the resulting mixture with a suitable amount of water, molding the resulting blend in the form of pellets or a honeycomb, with an extrusion molder, drying the molded article at a temperature in the range of 50° to 120° C., and thereafter calcining the dry molded article at a temperature in the range of 300° to 800° C., preferably 350° to 600° C., for one to 10 hours, preferably 2 to 6 hours under a current of air.
Optionally, 5 to 90% by weight, preferably 10 to 60% by weight, of the aforementioned component A may be substituted with activated carbon for the purpose of enabling the catalyst of this invention to substantially improve its activity in deodorization and ozone decomposition to a greater extent.
For this replacement, commercially available activated carbon can be employed. It may be used in a chemically or physically modified form of the activated carbon.
In the catalyst of this invention produced as described above, the component A is desired to account for a proportion in the range of 95 to 10% by weight and the activated carbon for a proportion in the range of 5 to 90% by weight.
From the component A, i.e. the TiO2 --SiO2, TiO2 --ZrO2, TiO2 --SiO2 --ZrO2, etc. prepared as described above, a final deodorant article can be obtained by the following method. For example, the deodorant is produced by thoroughly mixing TiO2 --SiO2 powder with activated carbon optionally further with a molding aid, blending the resulting mixture with a suitable amount of water, molding the resulting blend into an article of desired shape, then drying the article, and calcining the dry shaped blend when necessary. Though activated carbon is generally used in the form of powder, it may be used partly in the form of short fibers. The molding can be effected by any of the various known methods such as compression molding and extrusion molding.
The drying of the shaped composite article is effected at a temperature in the range of 50° to 200° C. and the calcining step is desirably carried out in a non-oxidizing atmosphere because the activated carbon is flammable. When the flammable substance is present in a low concentration, this calcination may none the less be carried out in the air.
The calcination is performed at a temperature in the range of 200° to 600° C., preferably 200° to 400° C., for a period of 1 to 10 hours, preferably 2 to 8 hours. When the calcination is not required, it can be omitted rather advantageously. Though the calcination performed at high temperatures results in improvement of the strength of the shaped composite article, it has the possibility of decreasing the specific surface area of the deodorant and lowering the deodorizing ability thereof.
The catalyst of the present invention which comprises the component A and the activated carbon may additionally incorporate therein a carrier such as alumina, silica, etc. or some other known deodorant.
The conversion of the component A to a final catalyst by the addition thereto of manganese, iron, nickel, cobalt, silver, platinum, palladium, or rhodium is effected by impregnating the shaped article of component A with an aqueous solution of the salt of the metal, drying and calcining the dry shaped article.
Alternatively, this conversion may be accomplished by adding the aqueous solution of metal salt in conjunction with a molding aid to the component A powder, kneading them, and molding the resulting blend.
Further, the catalyst of this invention permits additional use of a carrier. Examples of the material usable for the carrier are alumina, silica, silica-alumina, bentonite, diatomaceous earth, silicon carbide, titania, zirconia, magnesia, cordierite, mullite, pumice, activated carbon, and inorganic fibers. The combination of the catalyst with the carrier can be effected, for example, by preparing a slurry comprising the component A and other components of the catalyst and impregnating granular silicon carbide with the slurry thereby depositing the catalyst on the carrier. Other methods available for the production of the catalyst of this invention would be apparent to those skilled in the art.
The acceptable shapes of the catalyst article include not only the pellets and the honeycombs mentioned above but also cylinders, tubes, plates, ribbons, corrugated sheets, pipes, doughnuts, lattices, and monolithic shapes. lt is preferred to use the honeycomb form having a nominal diameter of penetration pores in the range of 0.7 to 3mm, wall thickness of cells in the range of 0.2 to 0 5mm, and aperture ratio thereof not less than 50%, preferably in the range of 50 to 80%. In case of using a deodorizing catalyst, the space availability of an ozone decomposition apparatus is also often limited Therefore, the reactor for catalyst is required to be small one. In any case it is desirable to avoid choking the catalyst bed with dust containing treated gas, or to avoid loss of pressure and to maintain a high activity of the catalyst. All of these requirements are satisfied by using a honeycomb catalyst as mentioned above. If the nominal diameter of penetration pore of catalyst is less than 0.7mm, not only loss of pressure but, choking of the catalyst bed tends to occur. If the diameter is above 3mm, it is not preferable to cause decreasing a ratio of ozone decomposition or deodorization on account of decreasing a geometric surface area. It is the same reason why the aperture ratio is required to be more than 50%.
The starting material for the component B which is used in combination with the component A in the catalyst of the present invention can be suitably selected from among oxides, hydroxides, inorganic acid salts, and organic acid salts, particularly ammonium salts, oxalates, nitrates, sulfates, and halogenates. Even when other binary through quaternary composite oxide is used as the component A, the deposition of the component B on a carrier is effected in the same manner as the TiO --SiO2 composite oxide.
The deodorizing catalyst contemplated by the present invention can be used for the treatment of any of various foul gases emanating from food storages, garbage dumps, septic tanks, sewage disposal plants, trash incinerators, cleaning shops, printing shops, painting shops, and chemical plants in general.
As examples of the component of offensive odor, there can be cited hydrogen sulfide, methyl sulfide, methyl mercaptan, methyl disulfide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isobutylamine, pyridine, acetone, methylethyl ketone, butyric acid, acetaldehyde, acrolein, phenol, benzene, xylene, toluene, and butenes. Gases containing these substances can be substantially completely deodorized by the method of this invention.
In the ozone-containing gas to be effectively treated by the catalyst of the present invention, the ozone concentration is roughly in the range of 0.01 to 10,000 ppm, though not critically.
The ozone decomposing agent of the present invention can be used for both gases and aqueous solutions containing ozone. The use of this agent is generally accomplished by passing a gas or solution under treatment through a bed packed with the ozone decomposing agent. The space velocity of the gas or solution for this passage generally falls in the range of 1,000 to 100,000 hr-1, preferably 3,000 to 50,000 hr-1.
The method, which uses packed beds of the ozone decomposition agent of this invention and packed beds of the conventional ozone decomposing agent in a multistage system brings about highly desirable results When a bed of activated carbon is used for the removal of ozone from a waste gas containing ozone in a high concentration, for example, the operation is hardly feasible because the bed may possibly encounter ignition and explosion and undergo heavy pulverization When a bed packed with the ozone decomposing agent of the present invention is set up on the upstream side of the path for the flow of the waste gas under treatment, the system enables the ozone concentration of the waste gas to be lowered in the former bed and permits the remaining ozone in the gas to be further removed in the latter activated carbon catalyst bed.
The deodorization of a foul gas by the use of the catalyst of this invention is accomplished by a method which comprises continuously introducing ozone at a prescribed rate into the foul gas containing a component of offensive odor and passing the resulting mixed gas over a bed of the catalyst set up on the downstream side in the path for the flow of the gas under treatment thereby effecting catalytic removal of the component of offensive odor from the gas under treatment. The concentration of the ozone introduced as described above into the foul gas is determined by the attributes and concentration of the component of offensive odor in the gas, other reaction conditions such as, for example, the reaction temperature, the kind of the catalyst, and the amount of the catalyst. This concentration is desired to fall in the range of 0.5 to 1,000 mols, preferably 1 to 10 mols, per mol of the component of offensive odor.
The reaction temperature is in the range of -10° to 400° C., preferably 0° to 300° C. The space velocity is in the range of 1,000 to 100,000 hr-1, preferably 3,000 to 50,000 hr-1.
Alternatively the deodorization of a foul gas by the present invention may be attained by a method which enables the deodorizing effect to be maintained for a long period by alternately repeating the first step of deodorizing the foul gas by removing the catalyst bed having adsorbed thereon a component of offensive odor from the gas stream and the second step of intermittently introducing ozone into the thus degenerated bed of catalyst thereby decomposing the adsorbate and regenerating the catalyst bed. The salient feature of this method resides in the fact that the introduction of ozone into the foul gas in motion of the purpose of regenerating the degenerated adsorbent can be effected without interrupting the flow of the gas under treatment. The ozone thus introduced fulfills the role of removing the component of offensive odor from the gas under treatment and, at the same time, removing the adsorbate from the catalyst bed by decomposition. Unlike the conventional method for effecting deodorization by adsorption, the method under discussion does not require operate alternate peration or two columns of adsorbent beds, one for the adsorption and the other for desorption and regeneration. For this method, it suffices to use only one column is needed to effect simultaneous treatments of adsorption and regeneration.
The conditions for the adsorption and regeneration are selected, depending on the composition of the gas under treatment and the concentration of the component of offensive odor. They can be found by a simple test. For example, the space velocity of the gas relative to the adsorbent is desirably fixed in the range of 100 to 1000 hr-1 and the concentration of ozone during the introduction thereof for regeneration in the range of 1 to 100 ppm. When the ozone concentration is lower than the range just mentioned, the regeneration is obtained with poor efficiency and traces of the foul order are detected. When the ozone concentration is higher than the range though the regeneration proceeds quickly, the unaltered portion of ozone passes into the ambient air and can also be readily detected.
The intermissions between and the durations of the intermittent introduction of ozone are desired to be each in the range of 30 minutes to 12 hours, per period of roughly one to 24 hours.
The intermittent introduction of ozone can be easily effected by programming the pattern of intermission in advance and combining an ozone generator and a timer in accordance with the programmed pattern.
Now, the present invention will be described more specifically below with reference to working examples. It should be noted, however, that this invention is not limited to these examples. The "ozone decomposition ratio" mentioned in the working examples was calculated by the following formula. ##EQU1##
The "deodorization ratio" similarly mentioned was calculated by the following formula. ##EQU2##
EXAMPLE 1
A composite oxide comprising titania and silica was prepared as follows. An aqueous sulfuric acid solution of titanyl sulfate having the following composition was used as a titanium source.
______________________________________                                    
TiOSO.sub.4 (as TiO.sub.2)                                                
                  250 g/liter                                             
Total H.sub.2 SO.sub.4                                                    
                1,100 g/liter                                             
______________________________________
Separately, 28 liters of aqueous ammonia (NH3, 25% ) were added to 40 liters of water and 2.4 kg of Snowtex-NCS-30 (silica sol containing about 30% by weight of silica as SiO2 ; product of Nissan Chemicals Industries Ltd.) were added further added thereto. To the resulting solution, a dilute titanium-containing aqueous sulfuric acid solution prepared by diluting 15.3 liters of the above aqueous sulfuric acid solution of titanyl sulfate with 30 liters of water was gradually added dropwise while under agitation to give rise to a coprecipitate gel. The resulting reaction mixture was left standing for 15 hours. The TiO2 --SiO2 gel thus obtained was separated by filtration, washed with water, and then dried at 200° C. for 10 hours.
The dry TiO2 --SiO2 gel was calcined under an atmosphere of air at 550° C. for six hours. The powder thus obtained had a composition of Ti2 :SiO2 =4:1 (molar ratio) and a BET surface area of 185m2 /g. The powder which will be referred to hereinafter as TS-1 was used to prepare an ozone decomposition catalyst as follows.
EXAMPLE 1A
In a kneader, 1.0 kg of the TS-1 powder was thoroughly mixed with 20 g of microcrystalline cellulose (produced by Asahi Chemical Industry Co., Ltd. and marketed under trademark designation of "Avicel") and a suitable amount of water. The resulting mixture was molded in the form of pellets 3.0 mm in diameter and 3.0 mm in length with an extrusion molding machine. The pellets were dried at 100° C. for 10 hours and then calcined under an atmosphere of air at 500° C. for six hours. Consequently, there was obtained a catalyst of formed TiO2 --SiO2.
EXAMPLE 2
TiO2 --ZrO2 was prepared as follows.
1.93 kg of zirconium oxychloride (ZrOCl2 8H2 O) was dissolved in 100 liters of cold water. In the resulting solution, 7.8 liters of an aqueous sulfuric acid solution of titanyl sulfate having the same composition as used in Example 1 was added and thoroughly mixed. The mixture thus formed was kept agitated at a temperature of about 30° C. and aqueous ammonia was gradually added thereto until the pH reached 7. The resulting reaction mixture was left standing at rest for 15 hours.
The TiO2 --ZrO2 gel thus obtained was separated by filtration, washed with cold water, and then dried at 200° C for 10 hours. Then, the dry gel was calcined under an atmosphere of air at 550° C. for six hours. The powder thus obtained had a composition of TiO2 :ZrO2 =4:1 (molar ratio) and a BET surface area of 140 m2 /g. The powder thus obtained will be referred to hereinafter as TZ-1.
By using this TZ-1 and following the procedure of Example 1A, there was obtained a catalyst formed of TiO2 --ZrO2.
EXAMPLE 3
TiO2 --SiO2 --ZrO2 by following the procedures of Examples 1,1A and 2. The powder thus obtained had a composition of TiO2 : SiO2 l : ZrO2 =80 : 16 :4 (molar ratio) and a BET surface area of 180m2 /g The powder thus obtained will be referred to hereinafter as TSZ-1.
By using this TSZ-1 and following the procedure of Example 1A, there was obtained a catlyst formed of TiO2 --SiO2 --ZrO2.
EXAMPLES 4-6
Catalysts formed of TiO2 --SiO2 were prepared by following the procedure of Example 1, except that the molar ratio of TiO2 / /SiO2 was varied.
The compositions and BET surface areas of the catalysts thus obtained were as shown in Table 1.
Control 1
A TiO2 powder was prepared by following the procedure of Example 1, except that use of silica sol was omitted. The TiO2 powder thus obtained had a BET surface area of 60 m2 /g. By using this powder and following the procedure of Example 1A, there was obtained a catalyst formed solely of TiO2.
Control 2
A powder solely of SiO2 containing no titanium was prepared by following the procedure of Example 1 The powder thus obtained had a surface area of 250 m2 /g By using this powder and following the procedure of Example 1 A, there was obtained a catalyst formed solely of SiO2.
Control 3
A TiO2 powder and a SiO2 powder obtained by following the procedures of Controls 1 and 2 were weighed out in amounts calculated to give a molar ratio of TiO2 / SiO2 =4 and thoroughly mixed. The mixed powder consequently obtained had a BET surface area of 90 m2 /g. By following the procedure of Example 1A, there was obtained a catalyst formed of the mixed powder.
EXAMPLE 7
The catalyts obtained in Examples 1-6 and Controls 1-3 were tested for ozone decomposition ratio as follows.
10.5 cc cf pellets of catalyst 3.0 mm in diameter and 3.0 mm in length were packed into a reaction tube made of Pyrex glass and having an inner diameter of 20 mm. Air containing 10 ppm of ozone was introduced to the bed of catalyst at a flow rate of 0.21 Nm3/ hr (space velocity 20,000 hr-1 with the reaction temperature varied in the range of 20° to 100° C., to find the ozone decomposition ratio.
The results were as shown in Table 2.
Example 8
In a kneader, 1.0 kg of the same TS-1 powder as used in Example 1 and an aqueous solution containing 0.366 kg of manganese nitrate, Mn(NO3)2 6H2 O, added thereto were thoroughly kneaded, with a suitable amount of water added thereto. By following the procedure of Example 1, the resulting mixture was molded in the form of pellets and the pellets were dried and calcined. Consequently, there was obtained a catalyst having a composition of TS-1 MnO2 =90 : 10 by weight ratio as oxide. X ray diffraction showed that manganese oxide obtained had the structure of beta-form manganese oxide. This catalyst was tested for ozone decomposition capacity by following the procedure of Example 7. The results were as shown in Table 3.
Examples 9-12
Catalysts were prepared by using the same TS-1 powder as used in Example 1 and following the procedure of Example 8, except that the component for addition to the component A was varied.
As catalyst sources, nitrates of iron, cobalt, nickel, and silver respectively were used.
The catalysts were tested for ozone decomposition capactiy by following the procedure of Example 7. The catalyst compositions and the results of the test were as shown in Table 3.
EXAMPLE 13
In an evaporation dish, 500 cc of the catalyst (pellets 3 mm in diameter and 3 mm in length ) formed of TiO2 --SiO2 obtained in Example 1 and 140 ml of an aqueous platinum nitrate solution containing 3.5 g of platinumion (Pt) were thoroughly mixed for impregnation of the catalyst by the solution. Over a water bath, the impregnated catalyst was concentrated and then dried at 120° C. for five hours. Then, the dry catalyst was calcined in an electric oven at 400° C. for three hours.
The catalyst thus obtained was tested for ozone decomposition capacity by following the procedure of Example 7. The results were as shown in Table 3.
EXAMPLES 14-15
Catalysts were prepared by following the procedure of Example 13, excepting palladium and rhodium respectively were used in the place of platinum.
These catalysts were tested for ozone decomposition catalyst by following the procedure of Example 7. The catalyst compositions and the results of the test were as shown in Table 3.
It is noted from the results of Tables 2 and 3 that the catalysts of this invention provide highly efficient decomposition of ozone at low temperatures not exceeding 50° C., particularly at temperatures approximating to normal room temperature.
              TABLE 1                                                     
______________________________________                                    
TiO.sub.2 /SiO.sub.2 catalyst                                             
           TiO.sub.2 /SiO.sub.2                                           
                    Specific area                                         
           (molar ratio)                                                  
                    (m.sup.2 /g)                                          
______________________________________                                    
Example 4    9          175                                               
Example 1    4          185                                               
Example 5    1          230                                               
Example 6    0.42       210                                               
______________________________________                                    

              TABLE 2                                                     
______________________________________                                    
Ozone decomposition ratio (%)                                             
Composition (mol ratio)                                                   
                    Reaction temperature (°C.)                     
TiO.sub.2   SiO.sub.2                                                     
                    ZrO.sub.2                                             
                            20    50     100                              
______________________________________                                    
Example 1                                                                 
        80      20      --    72    77     83                             
Example 2                                                                 
        80      --      20    70    74     81                             
Example 3                                                                 
        80      16       4    73    78     85                             
Example 4                                                                 
        90      10      --    71    75     81                             
Example 5                                                                 
        50      50      --    73    75     83                             
Example 6                                                                 
        30      70      --    70    73     77                             
Control 1                                                                 
        100     --      --    20    35     46                             
Control 2                                                                 
        --      100     --     0     0      3                             
Control 3                                                                 
        80      20      --    17    30     36                             
______________________________________                                    

              TABLE 3                                                     
______________________________________                                    
Ozone decomposition ratio (%)                                             
       Composition  Reaction temperature (°C.)                     
       (weight ratio)                                                     
                    20      50       100                                  
______________________________________                                    
Example 8                                                                 
         TS-1:MnO.sub.2 = 90:10                                           
                        90      94     97                                 
Example 9                                                                 
         TS-1:Fe.sub.2 O.sub.3 = 90:10                                    
                        89      93     96                                 
Example 10                                                                
         TS-1:CoO = 90:10                                                 
                        87      92     94                                 
Example 11                                                                
         TS-1:NiO = 90:10                                                 
                        85      92     95                                 
Example 12                                                                
         TS-1:AgO = 90:10                                                 
                        90      94     96                                 
Example 13                                                                
         TS-1:Pt = 99:1 94      97     99                                 
Example 14                                                                
         TS-1:Pd = 99:1 93      95     99                                 
Example 15                                                                
         Ts-1:Rh = 99:1 91      95     99                                 
______________________________________
EXAMPLE 16
A composite oxide comprising titanium and phosphorus was prepared as follows. An aqueous sulfuric acid solution of titanyl sulfate having the following composition was used as a titanium source.
______________________________________                                    
TiOSO.sub.4 (as TiO.sub.2)                                                
                  250 g/liter                                             
Total H.sub.2 SO.sub.4                                                    
                1,100 g/liter                                             
______________________________________
A titanium-containing aqueous sulfuric acid solution prepared by diluting 10 liters of the above aqueous sulfuric acid solution of titanyl sulfate with 50 liters of cold water was kept at 40° C. and, while under thorough agitation, 40 liters of an aqueous solution containing 4.13 kg of diammonium hydrogen phosphate were gradually added dropwise thereto, to give rise to a precipitate. The resulting reaction mixture was left standing at rest at 80° C. for six hours. The TiO2 --P2 O5 gel consequently obtained was separated by filtration, washed with cold water, and then dried at 150° C. for 10 hours.
Subsequently, the dry gel was calcined under an atmosphere of air at 550° C. for six hours. The powder consequently obtained had a composition of TiO2 : P2 O5 =2 : 1 (molar ratio) and a BET surface area of 70 m2 /g This powder will be referred to hereinafter as TPI and was used to prepare an ozone decomposition catalyst as follows
In a kneader, 1.0 kg of the TP-1 powder and 20 g of microcrystalline cellulose (produced by Asahi Chemical Industry Co., Ltd. and marketed under trademark designation of "Avicel") added thereto, were thoroughly mixed, with a suitable amount of water added thereto. The resulting mixture was molded in the form of pellets 3.0 mm in diameter and 3.0 mm in length with an extrusion molder. The pellets were dried at 100° C. for 10 hours and then calcined under an atmosphere of air at 500° C. for six hours. Consequently, there was obtained a catalyst formed of TiO2 --P2 O5.
EXAMPLE 17-19
Catalysts formed of TiO2 --P2 O5 were prepared by following the procedure of Example 1, ™except that the molar ratio of TiO2 --P2 O5 was varied.
The compositions and the BET surface areas of the catalysts obtained were as shown in Table 4.
              TABLE 4                                                     
______________________________________                                    
TiO.sub.2 --P.sub.2 O.sub.5 catalyst                                      
           TiO.sub.2 /P.sub.2 O.sub.5                                     
                    Specific area                                         
           (molar ratio)                                                  
                    (m.sup.2 /g)                                          
______________________________________                                    
Example 16   2          70                                                
Example 17   4          68                                                
Example 18   1          50                                                
Example 19   0.67       42                                                
______________________________________
EXAMPLE 20
The catalysts obtained in Examples 16-19 and Control 1 were tested for ozone decomposition ratio as follows.
10.5 cc of pellets of catalyst 3.0 in diameter and 3.0 mm in length were packed in a reaction tube made of Pyrex glass and having an inner diameter of 20mm. Air containing 10 ppm of ozone was introduced to the catalyst bed at a flow rate of 0.21 Nm3/ hr (space velocity 20,000 hr -1, with the reaction temperature varied in the range of ° to 100° C., to find the ozone decomposition ratio. The results were as shown in Table 5.
              TABLE 5                                                     
______________________________________                                    
Ozone decomposition ratio (%)                                             
Composition (molar                                                        
                  Reaction temperature(°C.)                        
ratio) TiO.sub.2 /P.sub.2 O.sub.5                                         
                  25       60       100                                   
______________________________________                                    
Example 16                                                                
        2             65       74     79                                  
Example 17                                                                
        4             63       72     77                                  
Example 18                                                                
        1             52       63     71                                  
Example 19                                                                
        0.67          48       60     68                                  
Control 1                                                                 
(only TiO.sub.2)                                                          
        25            38       46                                         
______________________________________
EXAMPLE 21
In a kneader, 1.0 kg of the same TP-1 powder as used in Example 16 and an aqueous solution containing 0.366 kg of manganese nitrate, Mn(NO3)2 6H2 O added thereto were thoroughly mixed, with a suitable amount of water added thereto. By following the procedure Example 16, the resulting mixture was molded in the form of pellets and the pellets were dried and calcined. Consequently, there was obtained a catalyst having the composition of TP-1 MnO2 =90 : 10 by weight ratio as oxide The catalyst was tested for ozone decomposition capacity by following the procedure of Example 20 The results were as shown in Table 6.
EXAMPLES 22-25
Catalysts were prepared by using the same TP-1 powder as used in Example 16 and following the procedure of Example 21, excepting the component for addition to the component A was varied.
As catalyst sources, nitrates of iron, cobalt, nickel, and silver respectively were used.
The catalysts were tested for ozone decomposition capacity by following the procedure of Example 20. The catalyst compositions and the results of the test were as shown in Table 6.
Example 26
500 cc of the catalyst (pellets 3 mm in diameter and 3 mm in length) formed of TiO2 --P2 O5 obtained in Example 16 and 140 ml of an aqueous platinum nitrate solution containing 3.5 g of platinum (Pt) were thoroughly mixed in an evaporation dish to effect impregnation of the catalyst with the solution. Over a water bath, the impregnated catalyst was concentrated and then dried at 120° C. for five hours. Then, the dry impregnated catalyst was calcined under an atmosphere of air at 400° C. for three hours.
The catalyst thus obtained had a composition of TP-1 : Pt =99 : 1.0 (weight ratio).
This catalyst was tested for ozone decomposition capacity by following the procedure of Example 20. The results were as shown in Table 6.
EXAMPLE 27-28
Catalysts were prepared by following the procedure of Example 26, except that palladium and rhodium were respectively used in the place of platinum.
The catalysts were tested for ozone decomposition capacity by following the procedure of Example 20. The catalyst compositions and the results of the test were as shown in Table 6. It is noted from the data of Tables 5 and 6 that the catalysts of the present invention provide highly efficient decomposition of ozone at low temperatures not exceeding 60° C., particularly at low temperature approximating to normal room temperature.
              TABLE 6                                                     
______________________________________                                    
Ozone decomposition ratio (%)                                             
       Composition Reaction temperature (°C.)                      
       (weight ratio)                                                     
                   25       60       100                                  
______________________________________                                    
Example 21                                                                
         TP-1:MnO.sub.2 = 90:10                                           
                       88       91     96                                 
Example 22                                                                
         TP-1:Fe.sub.2 O.sub.3 = 90:10                                    
                       87       90     96                                 
Example 23                                                                
         TP-1:CoO = 90:10                                                 
                       85       89     95                                 
Example 24                                                                
         TP-1:NiO = 90:10                                                 
                       82       89     95                                 
Example 25                                                                
         TP-1:Ag.sub.2 O = 90:10                                          
                       88       91     96                                 
Example 26                                                                
         TP-1:Pt = 99:1                                                   
                       94       97     99                                 
Example 27                                                                
         TP-1:Pd = 99:1                                                   
                       92       95     98                                 
Example 28                                                                
         TP-1:Rh = 99:1                                                   
                       90       94     98                                 
______________________________________
Example 29
In a kneader, 10 kg of the TS-1 powder obtained in Example 1 and a suitable amount of water added thereto were thoroughly mixed. The resulting mixture was thoroughly blended in a blender. The homogeneous mixture thus obtained was molded in the form of lattice-shaped honeycombs having visible dimensions of 50 mm in length, 50 mm in width, and mm in length (0.3 mm in wall thickness and 1.4 mm in mesh) with an extrusion molder. The honeycombs were dried at ° C. for five hours and then calcined under an atmosphere of air at 300° C. for two hours. Consequently, there was obtained a deodorizing catalyst formed of TS-lH.
EXAMPLE 30
A catalyst formed of TZ-1H was prepared by using the TZ-1 obtained in Example 2 and following the procedure of Example 29.
EXAMPLE 31
A catalyst formed of TSZ-1H was prepared by using the TSZ-1 obtained in Example 3 and following the procedure of Example 29.
EXAMPLES 32-34
Catalysts formed of TiO2 --SiO2 were prepared by following the procedure of Example 29, excepting the molar ratio of TiO2 /SiO2 varied. The compositions and the BET surface areas of the catalysts thus obtained were as shown in Table 7.
              TABLE 7                                                     
______________________________________                                    
TiO.sub.2 /SiO.sub.2 catalyst                                             
           TiO.sub.2 /SiO.sub.2                                           
                    Surface area                                          
           (molar ratio)                                                  
                    (m.sup.2 /g)                                          
______________________________________                                    
Example 32   9          175                                               
Example 29   4          185                                               
Example 33   1          230                                               
Example 34   0.42       210                                               
______________________________________
EXAMPLE 35
The catalysts obtained in Examples 29-34 were tested for deodorization ratio as follows.
250 ml of latticelike honeycombs of catalyst were packed in a reaction tube made of Pyrex glass. Steamsaturated air containing 5 ppm of trimethylamine or methyl mercaptan as a typical component of offensive odor was introduced to the catalyst bed at a flow rate of 5 Nm3 /hr (space velocity of 20,000 hr-1)
Ozone was introduced in a concentration of 20 ppm to the inlet side of the catalyst bed, with the reaction temperature at 5° C. After 500 hours' use of the catalyst bed required for stabilization of the catalyst activity, the catalyst was tested for deodorization ratio The results were as shown in Table 8.
              TABLE 8                                                     
______________________________________                                    
Deodorization ratio (%)                                                   
Composition (molar ratio)                                                 
                     Trimethyl-                                           
                               Methyl                                     
TiO.sub.2 --SiO.sub.2 --ZrO.sub.2                                         
                     amine     mercaptan                                  
______________________________________                                    
Example 29                                                                
        80:20:--         92        89                                     
Example 30                                                                
        80:--:20         90        89                                     
Example 31                                                                
        80:16:4          92        89                                     
Example 32                                                                
        90:10:--         93        89                                     
Example 33                                                                
        50:50:--         92        85                                     
Example 34                                                                
        30:70:--         92        85                                     
______________________________________
EXAMPLE 36
A catalyst having a composition of TS-1 MnO2 =90 : 10 by weight ratio as oxide was obtained by impregnating the lattice-like honeycombs of TS-1H of Example 29 with an aqueous manganese nitrate solution, drying the impregnated honeycombs, and then calcining them.
This catalyst was tested for deodorization capacity by following the procedure of Example 35. The results were as shown in Table 9. The ozone concentration in the outlet gas was less than 0.1 ppm.
EXAMPLE 37-43
Catalysts were prepared by following the procedure of Example 36, excepting the component for addition to the component A was varied.
Nitrates of iron, cobalt, nickel, silver, and platinum, and chlorides of palladium and rhodium were used as catalyst sources. The catalysts were tested for deodorization capacity by following the procedure of Example 35. The compositions of the catalysts and the results of the test were as shown in Table 9. The ozone concentrations in the outlet gases were invariably less than 0.1 ppm.
Controls 4-5
Catalysts were prepared by following the procedure of Example 36, excepting lattice-like honeycombs of activated alumina and lattice-like honeycombs of activated carbon were used in the place of TS-1H. The catalysts were tested for deodorization capacity by following the procedure of Example 35. The compositions of the catalysts and the results of the test were as shown in Table 9.
              TABLE 9                                                     
______________________________________                                    
Deodorization ratio (%)                                                   
Composition                    Methyl                                     
(weight ratio)     Trimethylamine                                         
                               mercaptan                                  
______________________________________                                    
Example 36                                                                
        TS-1:MnO.sub.2 = 90:10                                            
                       99          99                                     
Example 37                                                                
        TS-1:Fe.sub.2 O.sub.3 = 90:10                                     
                       95          98                                     
Example 38                                                                
        TS-1:CoO = 90:10                                                  
                       95          98                                     
Example 39                                                                
        TS-1:NiO = 90:10                                                  
                       95          97                                     
Example 40                                                                
        TS-1:AgO = 90:10                                                  
                       94          92                                     
Example 41                                                                
        TS-1:Pt = 99:1 93          91                                     
Example 42                                                                
        TS-1:Pd = 99:1 95          95                                     
Example 43                                                                
        TS-1:Rh = 99:1 94          91                                     
Control 4                                                                 
        --A.sub.2 O.sub.3 :MnO.sub.2 = 90:10                              
                       78          60                                     
Control 5                                                                 
        Activated carbon:                                                 
                       65          75                                     
        MnO.sub.2 = 90:10                                                 
______________________________________
As shown in Table 8 and Table 9, the catalysts of the present invention permit deodorization to be effected with high efficiency at such a low temperature as 5° C.
EXAMPLE 44
In a kneader, 750 g of the TS-1 powder obtained in Example 1 and 250 g of a commercially available activated carbon were thoroughly mixed, with a suitable amount of water added thereto. The resulting mixture was thoroughly blended in a blender. The homogeneous mixture thus obtained was molded in the form of pellets 5.0 mm in diameter and 6.0 mm in length with an extrusion molder. The pellets were dried at 150° C. for two hours. Consequently there was obtained an ozone decomposing agent formed of TiO2 --SiO2 --C.
EXAMPLE 45
An ozone decomposing agent formed of TiO2 --ZrO2 --C was prepared by using the TZ-1 obtained in Example 2 and following the procedure of Example 44.
EXAMPLE 46
An ozone decomposing agent formed of TiO2 --SiO2 ZrO2 --C was prepared by using the TSZ-1 obtained in Example 3 and following the procedure of Example 44.
EXAMPLE 47-49
Ozone decomposing agents formed of TiO2 --SiO2 --C were prepared by following the procedure of Example 44, except that the weight ratio of TiO2 --SiO2 to the activated carbon was varied. The compositions of the ozone decomposing agents thus obtained were as shown in Table 10.
Control 6
An ozone decomposing agent formed solely of activated carbon was prepared by following the procedure of Example 44, except that granular activated carbon was used in the place of the TS-1 powder.
EXAMPLE 50
The ozone decomposing agents obtained in Examples 44-49 and Control 6 were tested for ozone decomposition capacity as follows.
200 ml of pellets of the agent 5.0 mm in diameter and 6.0 mm in length were packed in a reaction tube made of Pyrex glass and having an inner diameter of 38 mm. Air containing 2,000 ppm of ozone and 2% of steam was introduced to the catalyst bed at a flow rate of 0.40 Nm3 /hr (space velocity 2,000 hr-1) at a reaction temperature of 20° C. The gas emanating from the catalyst bed was tested for ozone concentration.
The results obtained after 100 hours passage of the gas through the catalyst bed were as shown in Table 11.
              TABLE 10                                                    
______________________________________                                    
Ozone decomposing agent of TiO.sub.2 --SiO.sub.2 --C                      
            TiO.sub.2 --SiO.sub.2 :C                                      
            (% by weight)                                                 
______________________________________                                    
Example 47    90:10                                                       
Example 44    75:25                                                       
Example 48    50:50                                                       
Example 49    40:60                                                       
______________________________________                                    

              TABLE 11                                                    
______________________________________                                    
Outlet ozone concentration (ppm)                                          
______________________________________                                    
        Example 44                                                        
                0.5                                                       
        Example 45                                                        
                0.8                                                       
        Example 46                                                        
                0.4                                                       
        Example 47                                                        
                1.2                                                       
        Example 48                                                        
                1.0                                                       
        Example 49                                                        
                1.5                                                       
        Control 6                                                         
                3.4                                                       
______________________________________
EXAMPLE 51
In a kneader, 10 kg of the TS-1 powder obtained in Example 1 and 10 kg of commercially available activated carbon were thoroughly mixed, with a suitable amount of water added thereto. The resulting mixture was thoroughly blended in a blender. The homogeneous mixture thus obtained was molded in the form of lattice-like honeycombs having visible dimensions of 50 mm in length, 50 mm in width, and 20 mm in depth (0.7 mm in wall thickness and 3.0 mm in mesh) with an extrusion molder. The honeycombs were dried at 150° C. for five hours and then calcined under an atmosphere of air at 300° C. for two hours. Consequently, there was obtained a deodorant formed of TiO2 --SiO2 --C.
EXAMPLE 52
A deodorant formed of TiO2 --ZrO2 --C was prepared by using the TZ-1 obtained in Example 2 and following the procedure of Example 51.
EXAMPLE 53
A deodorant formed of TiO2 --SiO2 --ZrO2 --C was prepared by using the TSZ-1 obtained in Example 3 and following the procedure of Example 51.
EXAMPLES 54-56
Deodorants formed of TiO2 --SiO2 --C were prepared by following the procedure of Example 51, excepting the weight ratio of the TiO2 --SiO2 and the activated carbon was varied. The compositions of the deodorants consequently obtained were as shown in Table 12.
Control 7
A deodorant formed solely of activated carbon was prepared by following the procedure of Example 51, except that powdered activated carbon was used in the place of the TS-1 powder.
EXAMPLE 57
The various deodorants obtained in Example 51-56 and Control 7 were tested for capacity for deodorization of a foul gas as follows. A deodorant was placed in a container having an inner volume of 2 liters. Air (20° C.) containing 300 ppm of ammonia or hydrogen sulfide was introduced to the deodorant. The deodorant covered with the air was left standing at rest. At intervals of 30 minutes, 60 minutes, and 90 minutes, the air was tested for residual ammonia or hydrogen sulfide concentration to determine deodorization ratio. The results of the test were as shown in Table 13.
              TABLE 12                                                    
______________________________________                                    
Composition of TiO.sub.2 --SiO.sub.2 --C deodorant                        
            TiO.sub.2 --SiO.sub.2 :C                                      
            (% by weight)                                                 
______________________________________                                    
Example 54    90:10                                                       
Example 55    75:25                                                       
Example 51    50:50                                                       
Example 56    25:75                                                       
______________________________________                                    

              TABLE 13                                                    
______________________________________                                    
Deodorization ratio (%)                                                   
Ammonia             Hydrogen sulfide                                      
After       After   After   After  After After                            
30 min.     60 min. 90 min. 30 min.                                       
                                   60 min.                                
                                         90 min.                          
______________________________________                                    
Example 51                                                                
        90      95      ≃100                                
                              80     95    ≃100             
Example 52                                                                
        85      95      ≃100                                
                              80     95    ≃100             
Example 53                                                                
        90      95      ≃100                                
                              80     95    ≃100             
Example 54                                                                
        ≃100                                                
                ≃100                                        
                        ≃100                                
                              50     70    90                             
Example 55                                                                
        90      95      ≃100                                
                              70     90    95                             
Example 56                                                                
        80      90      95    80     95    ≃100             
Control 57                                                                
        20      35      50    80     95    ≃100             
______________________________________
EXAMPLE 58
The various deodorants obtained in Examples 51, 54, 55, and 56 and Control 7 were tested for crush strength with an Instron tester The results were as shown in Table 14.
              TABLE 14                                                    
______________________________________                                    
Crush strength (kg/cm.sup.2)                                              
______________________________________                                    
        Example 51                                                        
                8                                                         
        Example 54                                                        
                12                                                        
        Example 55                                                        
                10                                                        
        Example 56                                                        
                5                                                         
        Control 7                                                         
                1.5                                                       
______________________________________
EXAMPLE 59
A tube made of Pyrex glass was packed with the lattice-like honeycombs of catalyst TS-1H obtained in Example 29 so as to preclude the incoming gas from finding a short path. Air containing 5 ppm of trimethylamine as a typical component of offensive odor was continuously introduced at a flow rate of 2.5 Nm3 /hr to the catalyst bed at 25° C. After 10 hours' use of the catalyst bed, the gas at the outlet of the catalyst bed was analyzed to determine trimethylamine concentration. Then the flow of the gas was continued. After the catalyst bed was exhausted and the concentration of the component of offensive odor in the gas at the outlet of the catalyst bed roughly equalled the concentration at the inlet, introduction of ozone to the tube interior was started. The introduction of ozone was adjusted so that the ozone concentration in the gas would remain at 30 ppm. The ozone introduction was continued for five hours. At the end of the ozone introduction, the gas at the outlet of the catalyst bed was analyzed for ozone and trimethylamine contents. Thereafter, the ozone introduction was discontinued and the introduction of the gas containing the component of offensive odor was continued to effect degeneration of the catalyst bed for 10 hours. At the end of the degeneration, the 9as at the outlet of the catalyst bed was analyzed. Then, the same operation of intermittently introducing ozone to the exhausted catalyst bed as described above was repeated a total of 10 times After elapse of 10 hours, the gas at the outlet of the Catalyst bed was analyzed.
The analysis for trimethylamine was made by using a FID-fitted gas chromatography and that for ozone an ozone monitor. The results were as shown in Table 15.
EXAMPLE 60
The catalyst obtained in Example 59 was subjected to the procedure of Example 59, except that the temperature of the catalyst bed was kept at 0° C.
The results were as shown in Table 16.
EXAMPLE 61
The catalyst of TZ-1H obtained in Example 30 was tested for adsorption and regeneration by following the procedure of Examples 59 and 60. The results were as shown in Tables 15 and 16.
EXAMPLE 62
The catalyst of TSZ-1H obtained in Example 31 was tested for adsorption and regeneration by following the procedure of Examples 59 and 60. The results were as shown in Tables 15 and 16.
              TABLE 15                                                    
______________________________________                                    
Results of analysis of outlet gas of                                      
catalyst be performed at 25° C.                                    
               Outlet gas concen-                                         
                             Gas concen-                                  
Outlet gas     tration during first                                       
                             tration after                                
concentration  cycle of ozone                                             
                             10 cycles of                                 
after 10 hours'                                                           
               introduction (ppm)                                         
                             regeneration                                 
operation (ppm)                                                           
               Trimethyl-        (ppm)                                    
Trimethylamine amine     Ozone   Trimethylamine                           
______________________________________                                    
Example                                                                   
       ND          ND        1.0   ND                                     
59                                                                        
Example                                                                   
       2.0         ND        5.0   2.0                                    
61                                                                        
Example                                                                   
       1.0         ND        3.0   1.0                                    
62                                                                        
______________________________________                                    
 ND: Not more than 0.1 ppm                                                

              TABLE 16                                                    
______________________________________                                    
Results of analysis of outlet gas of                                      
catalyst bed performed at 0° C.                                    
               Outlet gas concen-                                         
                             Gas concen-                                  
Outlet gas     tration during first                                       
                             tration after                                
concentration  cycle of ozone                                             
                             10 cycles of                                 
after 10 hours'                                                           
               introduction (ppm)                                         
                             regeneration                                 
operation (ppm)                                                           
               Trimethyl-        (ppm)                                    
Trimethylamine amine     Ozone   Trimethylamine                           
______________________________________                                    
Example                                                                   
       ND          ND        3.0   ND                                     
60                                                                        
Example                                                                   
       1.0         ND        8.0   1.0                                    
61                                                                        
Example                                                                   
       0.5         ND        6.0   0.5                                    
62                                                                        
______________________________________                                    
 ND: Not more than 0.1 ppm
EXAMPLE 63
A catalyst having a composition of TS-1 : MnO2 =90 : 10 in weight ratio as oxide was obtained by impregnating the lattice-like honeycombs of TS-1H obtained in Example 29 with an aqueous manganese nitrate solution, and drying and calcining the impregnated honeycombs. This catalyst was tested for adsorption and regeneration by following the procedure of Example 60, excepting the concentration of the introduced ozone was fixed at 20 ppm and the duration of the introduction was two hours. The results of the test were as shown in Table 17.
EXAMPLE 64
The catalyst obtained in Example 63 was tested for adsorption and regeneration by following the procedure of Example 63, excepting the catalyst bed temperature was fixed at 25° C. The results were as shown in Table 18.
EXAMPLES 65-71
Adsorbents were prepared by following the procedure of Example 63, excepting the component B for addition to the component A was varied.
As raw materials for the component B, nitrates of iron, cobalt, nickel, silver, and platinum and chlorides of palladium and rohdium were used.
The catalysts thus obtained were tested for adsorption and regeneration by following the procedure of Example 63 The catalyst compositions and the results of the test were as shown in Table 17.
EXAMPLE 72-78
The catalysts obtained in Examples 65-71 were tested for adsorption and regeneration by following the procedure of Example 64 The catalyst compositions and the results of the test were as shown in Table 18.
Controls 8-9
Catalyst were prepared by following the procedure of Example 63, except that lattice-like honeycombs of activated alumina and lattice-like honeycombs of activated carbon were used in the place of the TS-1H.
The catalysts were tested for adsorption and regeneration by following the procedure of Example 64. The catalyst compositions and the results of the test were as shown in Table 18.
                                  TABLE 17                                
__________________________________________________________________________
Results of analysis of outlet gas of adsorbent bed performed at 0° 
C.                                                                        
             Outlet gas concen-                                           
                        Outlet gas concentration                          
                                     Gas concentration                    
             tration after 10 hours'                                      
                        during first cycle of                             
                                     after 10 cycles                      
Composition  operation (ppm)                                              
                        ozone introduction (ppm)                          
                                     of regeneration (ppm)                
(weight ratio)                                                            
             Trimethylamine                                               
                        Trimethylamine                                    
                                Ozone                                     
                                     Trimethylamine                       
__________________________________________________________________________
Example 63                                                                
      TS-1:MnO.sub.2                                                      
             ND         ND      ND  ND                                    
      90:10                                                               
Example 65                                                                
      TS-1:Fe.sub.2 O.sub.3                                               
             ND         ND      1.0 ND                                    
      90:10                                                               
Example 66                                                                
      TS-1:CoO                                                            
             ND         ND      1.5 ND                                    
      90:10                                                               
Example 67                                                                
      TS-1:NiO                                                            
             ND         ND      1.1 ND                                    
      90:10                                                               
Example 68                                                                
      TS-1:AgO                                                            
             ND         ND      0.2 ND                                    
      90:10                                                               
Example 69                                                                
      TS-1:Pt                                                             
             ND         ND      ND  ND                                    
      99.5:0.5                                                            
Example 70                                                                
      TS-1:Pd                                                             
             ND         ND      ND  ND                                    
      99.5:0.5                                                            
Example 71                                                                
      TS-1:Rh                                                             
             ND         ND      ND  ND                                    
      99.5:0.5                                                            
__________________________________________________________________________
 ND: Not more than 0.1 ppm                                                

                                  TABLE 18                                
__________________________________________________________________________
Results of analysis of outlet gas of catalyst bed performed at 25° 
C.                                                                        
              Outlet gas concen-                                          
                         Outlet gas concentration                         
                                      Gas concentration                   
              tration after 10 hours'                                     
                         during first cycle of                            
                                      after 10 cycles                     
Composition   operation (ppm)                                             
                         ozone introduction (ppm)                         
                                      of regeneration (ppm)               
(weight ratio)                                                            
              Trimethylamine                                              
                         Trimethylamine                                   
                                 Ozone                                    
                                      Trimethylamine                      
__________________________________________________________________________
Example 64                                                                
      TS-1:MnO.sub.2                                                      
              ND         ND      ND   ND                                  
      90:10                                                               
Example 72                                                                
      TS-1:Fe.sub.2 O.sub.3                                               
              ND         ND      0.5  ND                                  
      90:10                                                               
Example 73                                                                
      TS-1:CoO                                                            
              ND         ND      0.8  ND                                  
      90:10                                                               
Example 74                                                                
      TS-1:NiO                                                            
              ND         ND      0.6  ND                                  
      90:10                                                               
Example 75                                                                
      TS-1:AgO                                                            
              ND         ND      0.1  ND                                  
      90:10                                                               
Example 76                                                                
      TS-1:Pt ND         ND      ND   ND                                  
      99.5:0.5                                                            
Example 77                                                                
      TS-1:Pd ND         ND      ND   ND                                  
      99.5:0.5                                                            
Example 78                                                                
      TS-1:Rh ND         ND      ND   ND                                  
      99.5:0.5                                                            
Control 8                                                                 
      --Al.sub.2 O.sub.3 :MnO.sub.2                                       
              4.0        3.0     10.0 4.5                                 
      90:10                                                               
Control 9                                                                 
      Activited                                                           
              ND         2.0     ND   4.0                                 
      carbon:MnO.sub.2                                                    
      90:10                                                               
__________________________________________________________________________
 ND: Not more than 0.1 ppm
EXAMPLES 79-80
Catalysts were prepared by following the procedure of Example 8, except that amount of manganese nitrate addition was varied. Thus there were obtained catalysts having compositions of TS-1 MnO2 =80:20 by weight ratio as oxide and that of TS-1: MnO0 =70 : 30 by weight ratio as oxide.
EXAMPLE 81
A catalyst was prepared by following the procedure of Example 8, except that TiO2 --SiO2 (composition of TiO2 /--SiO2 =1, molar ratio) obtained in Example 5 was used in place of TS-1. Thus there was obtained a catalyst having a composition of TiO2 --SiO2 : MnO2 =90:10 by weight ratio as oxide.
EXAMPLE 82
A catalyst was prepared by following the procedure of Example 8, except that TiO2 --SiO2 (composition of TiO2 --/SiO2 =0.42) obtained in Example 6 was used in place of TS-1. Thus there was obtained a catalyst having a composition of TiO2 --SiO2 : MnO2 =90:10 by weight ratio as oxide.
EXAMPLE 83-86
The catalysts prepared in Examples 79-82 were tested for the activity of ozone decomposition by following the procedure of Example 20. The reaction temperature was at 2° C. The results were as shown in Table 19.
              TABLE 19                                                    
______________________________________                                    
Ozone decomposition ratio (%)                                             
                           Ozone                                          
Catalyst      Composition  decomposition                                  
used          (weight ratio)                                              
                           ratio (%)                                      
______________________________________                                    
Example 83                                                                
        Example 79                                                        
                  TS-1:MnO.sub.2                                          
                               90                                         
                  80:20                                                   
Example 84                                                                
        Example 80                                                        
                  TS-1:MnO.sub.2                                          
                               91                                         
                  70:30                                                   
Example 85                                                                
        Example 81                                                        
                  TiO.sub.2 --SiO.sub.2 :MnO.sub.2                        
                               84                                         
                  90:10                                                   
Example 86                                                                
        Example 82                                                        
                  TiO.sub.2 --SiO.sub.2 :MnO.sub.2                        
                               82                                         
                  90:10                                                   
______________________________________
EXAMPLES 87-90
The catalysts prepared in Example 79-82 were tested for deodorizing activity by following procedure of Example 35, excepting 10.5 ml of pellets of catalysts were packed in a reaction tube made of Pyrex glass having an inner diameter of 20 mm, and steam saturated air containing ppm of trimethylamine and methyl mercaptan was introduced to the catalyst bed at a flow rate of 0.21 Nm3 /hr (space velocity of 20,000 hr-1)at a reaction temperature of 2° C. The results obtained were as shown in Table 20.
              TABLE 20                                                    
______________________________________                                    
Deodorization ratio (%)                                                   
                           Tri-     Methyl-                               
Catalyst      Composition  methyl-  mer-                                  
used          (weight ratio)                                              
                           amine    captan                                
______________________________________                                    
Example 87                                                                
        Example 79                                                        
                  TS-1:MnO.sub.2                                          
                               99     99                                  
                  80:20                                                   
Example 88                                                                
        Example 80                                                        
                  TS-1:MnO.sub.2                                          
                               99     99                                  
                  70:30                                                   
Example 89                                                                
        Example 81                                                        
                  TiO.sub.2 --SiO.sub.2 :MnO.sub.2                        
                               93     94                                  
                  90:10                                                   
Example 90                                                                
        Example 82                                                        
                  TiO.sub.2 --SiO.sub.2 :MnO.sub.2                        
                               94     96                                  
                  90:10                                                   
______________________________________
EXAMPLES 91-92 AND CONTROL 10
The catalysts obtained in Examples 36, 42 and Control 4 were tested for durability as follows: In a reaction tube made of Pyrex glass, 250 cc of lattice-like honeycombs of catalyst were packed. Air containing 40% of relative humidity, and containing 5 ppm of ozone was introduced to the catalyst bed at a flow rate of 12.5Nm3 /hr (space velocity 50,000hr-1) at room temperature. Change of ozone decomposition ratio with time was tested for days. The results were shown in Table 21.
              TABLE 21                                                    
______________________________________                                    
Ozone decomposition ratio (%) with time                                   
Catalyst      After    After   After  After                               
used          1 day    50 days 100 days                                   
                                      250 days                            
______________________________________                                    
Example 91                                                                
        Example 36                                                        
                  99.9     95.8  93.1   91.5                              
Example 92                                                                
        Example 42                                                        
                  99.9     94.3  91.2   90.7                              
Control 10                                                                
        Control 4 88.7     67.3  43.2   32.7                              
______________________________________
EXAMPLE 93
A composite oxide comprising titania and silica was prepared as follows. An aqueous sulfuric acid solution of titanyl sulfate having the following composition was used as a titanium source.
______________________________________                                    
TiOSO.sub.4 (as TiO.sub.2)                                                
                  250 g/liter                                             
Total H.sub.2 SO.sub.4                                                    
                1,100 g/liter                                             
______________________________________
Separately, 280 liters of aqua ammonia (NH3, 25%) was added to 400 liters of water and 24 kg of Snowtex-NCS-30 (silica sol containing about 30% by weight of silica as SiO2 ; product of Nissan Chemicals Industries Ltd.) was added further added thereto. To the resulting solution, a titanium-containing aqueous sulfuric acid solution prepared by diluting 153 liters of the above aqueous sulfuric acid solution of titanyl sulfate with 300 liters of water was gradually added dropwise while under agitation to give rise to a co-precipitate gel. The resulting reaction mixture was left standing at rest for 15 hours. The TiO2 --SiO2 gel thus obtained was separated by filtration, washed with water, and then dried at 200° C. for 10 hours.
The dry TiO2 --SiO2 gel was calcined under an atmosphere of air at 550° C. for six hours. The powder thus obtained had a composition of TiO2 :SiO2 =4:1 (molar ratio) and a BET surface area of 185m2 /g The powder thus obtained was used to prepare deodorant formed of lattice-like honeycomb.
An aqueous solution containing 3.66 kg of manganese nitrate Mn(NO3)2 6H2 O was added in 10 kg of this powder. And then the resulting mixture was thoroughly blended in a blender with a suitable amount of water added thereto. The homogeneous mixture thus obtained was molded in the form of lattice-like honeycombs having visible dimensions of 50 mm in length, 50 mm in width, and 100 mm in depth with an extrusion molder. The honeycombs were dried at 150° C. for five hours and then calcined under an atmosphere of air at 300° C. for two hours The honeycomb obtained had penetration pores 1 4mm in individual diameter of wall thickness of cells of 0.33 mm and the aperture ratio of this honeycomb was 64% There was obtained a catalyst formed of the honeycombs having a composition of TiO2 --SiO2 =90:10 by weight ratio as oxide.
EXAMPLE 94-95
Catalysts formed of lattice-like honeycombs were prepared by using the same composition as used in Example 93 and following the procedure of Example 93, excepting the form of catalysts were varied
The diameter of penetration pores, wall thickness of cells, and aperture ratio of catalysts thus obtained were shown as follows.
______________________________________                                    
       Diameter penetra-                                                  
                   Wall thickness                                         
                               Aperture                                   
       tion pores (mm)                                                    
                   of cells (mm)                                          
                               ratio (%)                                  
______________________________________                                    
Example 94                                                                
         2.3           0.42        70                                     
Example 95                                                                
         1.0           0.25        63                                     
______________________________________
EXAMPLE 96-98
The catalysts obtained in Examples 93-95 were tested for deodorization and loss of pressure at the time as follows.
250 ml of lattice-like honeycombs of catalyst were packed in a reaction tube made of Pyrex glass. Steamsaturated air containing 5 ppm of trimethylamine or methyl mercaptan as a typical component of offensive odor was introduced to the catalyst bed at a flow rate of 5 Nm3 /hr (space velocity of 20,000 hr-1).
Ozone was introduced in a concentration of 20 ppm to the inlet side of the catalyst bed, with the reaction temperature at 5° C. After 500 hours' use of the catalyst bed required for stabilization of the catalyst activity, the catalyst was tested for deodorization ratio. The losses of pressure were tested at above-mentioned operating condition. The results were as shown in Table 22.
              TABLE 22                                                    
______________________________________                                    
Deodorization ratio (%) and loss of pressure (mmH.sub.2 O)                
deodorization ratio (%)                                                   
            Tri-     Methyl  Pressure                                     
                                     Linear                               
Catalyst    methyl-  mer-    drop    velocity                             
used        amine    captan  (mmH.sub.2 O)                                
                                     (m/sec)                              
______________________________________                                    
Example                                                                   
       Example  99       99    20      0.87                               
96     93                                                                 
Example                                                                   
       Example  95       98     7      0.79                               
97     94                                                                 
Example                                                                   
       Example  99       99    39      0.89                               
98     95                                                                 
______________________________________

Claims (10)

What claimed is:
1. A method for the purification of an ozone-containing gas, which comprises passing said ozone-containing gas through a bed of a catalyst consisting of a component A composed of 95 to 10% by weight of a composite oxide and between 5 and 90% by weight of activated carbon said composite oxide comprising 20 to 95 mol% of (a) TiO2 and 5 to 80 mol% of (b) at least one oxide selected from the group consisting of SiO2, ZrO2 and P2 O5.
2. A method of according to claim 1, wherein said component A is selected from the group consisting of TiO2 --SiO2, TiO2 --ZrO2, TiO2 --P2 O5, TiO2 --SiO2 --ZrO2, TiO2 --SiO2 --P2 O5, TiO2 --ZRO2 --P2 O5, and TiO2 --SiO2 --ZrO2 --P2 O5.
3. A method for the purification of an ozone-containing gas, which comprises passing said ozone-containing gas through a bed of the catalyst consisting of a component A composed of 95-10% by weight of a composite oxide containing (a) titanium and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus, between 5 and 90% by weight of activated carbon, and a component B composed of at least one element selected from the groups consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of said component B for a proportion in the range of not more than 150 by weight of oxide where said element selected if manganese, iron, cobalt, nickel or silver or in the range of not more than 10 parts by weight as metal where said element is platinum, palladium, or rhodium, respectively based on 100 parts by weight of said component A as oxide, thereby effecting decomposition of the ozone in said gas.
4. A method for the purification of a gas containing a component of offensive odor, selected from the group consisting essentially of hydrogen sulfide, methyl sulfide, methyl mercaptan, methyl disulfide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isobutylamine, pyridine, acetone, methylethylketone, butyric acid, acetaldehyde, acrolein, phenol, benzene, xylene, toluene, and butenes, which comprises combining said gas with ozone to a level of 1 to 10 mol per mol of component to offensive odor and passing the resultant mixed gas through a bed of a catalyst comprising a component A composed of 95 to 10% by weight a composite oxide containing (a) 20 to 95 mol% of TiO2, and (b) 5-80 mol% of at least one element selected from the group consisting of silicon, zirconium, and phosphorus and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of said component B for a proportion is in the range of not more than 150 parts by weight as oxide where said element selected is manganese, iron, cobalt, nickel, or silver or in the range of not more than 10 parts by weight as metal where said element is platinum, palladium, or rhodium, respectively based on 100 parts by weight of said component A as oxide thereby effecting decomposition and removal of said component of offensive odor by the ozone.
5. A method for the purification of a gas containing a component of offensive odor, selected from the group consisting essentially of hydrogen sulfide, methyl sulfide, methyl mercaptan, methyl disulfide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isobutylamine, pyridine, acetone, methylethylketone, butyric acid, acetaldehyde, acrolein, pheon, benzene, xylene, toluene, and butenes, which comprises combining said gas with ozone to a level of about 1 to 10 mol ozone per mol of components having offensive odor and passing the resultant mixed gas through a bed of the catalyst consisting of a component A composed of 95-10% by weight of a composite oxide containing (a) titanium and (b) at least one elment selected from the group consisting of silicon, zirconium, and phosphorus, between 5 and 90% by weight of activated carbon, and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of said component B for a proportion in the range of not more than 150 by weight of oxide where said element selected if manganese, iron, cobalt, nickel or silver or in the range of not more than 10 parts by weight as metal where said element is platinum, palladium, or rhodium, respectively based on 100 parts by weight of said component A as oxide thereby effecting removal of said component of offensive odor by the ozone.
6. A method for the purification of an ozone-containing gas, which comprises passing said ozone-containing gas through a bed of the catalyst consisting of a component A composed of 95 to 10% by weight a composite oxide containing (a) 20 to 95 mol% TiO2 and 5 to 80 mol% of (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus, and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of said component B for a proportion is in the range of not more that 150 parts by weight of oxide where said element selected is manganese, iron, cobalt, nickel or silver or in the range of not more than 10 parts by weight as metal where said element is platinum, palladium or rhodium, respectively based on 100 parts by weight of said component A as oxide, thereby effecting decomposition of the ozone in said gas.
7. A method for the purification of a gas containing a component of offensive odor, selected from the group consisting essentially of hydrogen sulfide, methyl sulfide, methyl mercaptan, methyl disulfide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isobutylamine, pyridine, acetone, methylethylketone, butyric acid, acetaldehyde, acrolein, phenol, benzene, xylene, toluene, and butenes, which comprises
i) deodorizing said gas by passing it through a bed of catalyst comprising a component consisting of a component A composed of a composite oxide containing (a) titanium, and (b) at least one element selected from the group consisting of silicon, zirconium, and phosphorus and a component B composed of at least one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of said component B for a proportion is in the range of not more than 150 parts by weight as oxide where said element selected is manganese, iron, cobalt, nickel, or silver or in the range of not more than 10 parts by weight as metal where said element is platinum, palladium, or rhodium, respectively based on 100 parts by weight of said component A as oxide
ii) removing said catalytic bed from the gas stream the bed having absorbed thereon said component of offensive odor and
iii) introducing ozone intermittently into the catalyst bed while removed from the gas stream to decompose said component of offensive odor and regenerate said bed.
8. A method according to claim 7, wherein said component A is selected from the group consisting of TiO2 --SiO2, TiO2 --ZrO2, TiO2 --P2 O5, TiO2 --SiO2 --ZeO2, TiO2 --SiO2 --P2 P5, TiO2 --ZrO2 --P2 O5, and TiO2 --SiO2 --ZrO2 --P(hd 2O5.
9. A method according to claim 8, wherein said component A comprises 20 to 95 mol% of TiO2 and 5 and 80 mol% of at least one oxide selected from the group consisting of SiO2, ZrO2 and P2 O5.
10. A method according to claim 7 wherein said catalyst consists of a component A composed of 95-10% by weight of an oxide containing (a) 20 to 95 mol% by weight of an oxide containing (a) 20 to 95 mol% TiO2 and (b) 5-80 mol% of the oxide of at least one element selected from the group consisting of silicon, zirconium, and phosphorus, between 5 and 95% by weight of activated carbon and a component B composed of at lest one element selected from the group consisting of manganese, iron, cobalt, nickel, silver, platinum, palladium, and rhodium, wherein the amount of said component B for a proportion in the range of not more than 150 parts by weight as oxide where said element selected is manganese, iron, cobalt, nickel, or silver or in the range of not more than 10 parts by weight as metal where said element is platinum, palladium, or rhodium, respectively based on 100 parts by weight of said component A as composite oxide.
US07/684,983 1987-01-21 1991-04-15 Method for purification of gas Expired - Fee Related US5145657A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP62-10008 1987-01-21
JP62010008A JPH0741146B2 (en) 1987-01-21 1987-01-21 Deodorization method
JP62011247A JPS63181764A (en) 1987-01-22 1987-01-22 Deodorizing method
JP62-11247 1987-01-22

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US07549828 Continuation 1990-08-09

Publications (1)

Publication Number Publication Date
US5145657A true US5145657A (en) 1992-09-08

Family

ID=26345158

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/684,983 Expired - Fee Related US5145657A (en) 1987-01-21 1991-04-15 Method for purification of gas

Country Status (5)

Country Link
US (1) US5145657A (en)
EP (1) EP0275620B1 (en)
KR (1) KR880008830A (en)
DE (1) DE3781134T2 (en)
ES (1) ES2033838T3 (en)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5212140A (en) * 1991-02-28 1993-05-18 Sakai Chemical Industry Co., Inc. Catalyst for decomposing ozone
US5403548A (en) * 1992-02-28 1995-04-04 Takeda Chemical Industries Ltd. Activated carbon adsorbent and applications thereof
US5422331A (en) * 1994-02-25 1995-06-06 Engelhard Corporation Layered catalyst composition
US5472676A (en) * 1989-05-11 1995-12-05 Nippon Shokubai Co., Ltd. Method of deodorizing a gas containing maloderous components
US5683532A (en) * 1990-08-12 1997-11-04 Kabushiki Kaisha Seibu Giken Method of manufacturing an active silica gel honeycomb adsorbing body usable in an atmosphere having 100% relative humidity
US5829066A (en) * 1990-11-19 1998-11-03 Takeda Chemical Industries, Ltd. Deodorizing apparatus and a toilet provided with the apparatus
US5849256A (en) * 1996-04-26 1998-12-15 Engelhard Corporation Method for oxidizing carbon monoxide in a gas stream containing oxidizable sulphur compounds
US5997831A (en) * 1996-07-12 1999-12-07 Engelhard Corporation Method of catalytically treating the atmosphere and heat exchange devices produced thereby
US6156283A (en) * 1998-03-23 2000-12-05 Engelhard Corporation Hydrophobic catalytic materials and method of forming the same
US6200542B1 (en) 1995-01-20 2001-03-13 Engelhard Corporation Method and apparatus for treating the atmosphere
US6214303B1 (en) 1995-01-20 2001-04-10 Engelhard Corporation Method and apparatus for treating the atmosphere
US6340066B1 (en) 1995-01-20 2002-01-22 Engelhard Corporation Pollutant treating devices and methods of making the same
US6375904B1 (en) 1999-12-20 2002-04-23 Airtex Manufacturing, Inc. Wastewater collection system gas emission control
US6517899B1 (en) 1995-01-20 2003-02-11 Engelhard Corporation Catalyst and adsorption compositions having adhesion characteristics
US20030166466A1 (en) * 1995-01-20 2003-09-04 Hoke Jeffrey B. Catalyst and adsorption compositions having improved adhesion characteristics
US6712879B2 (en) * 2001-09-28 2004-03-30 Kabushiki Kaisha Toshiba Carbon dioxide gas absorbent and carbon dioxide gas separating apparatus
US20040146442A1 (en) * 2003-01-28 2004-07-29 Shu-Sung Lin Method and apparatus for treating waste gas containing PFC and/or HFC
US20040156767A1 (en) * 2001-04-12 2004-08-12 Industrial Technology Research Institute Process and apparatus for treating contaminated gas
US6818254B1 (en) 1995-01-20 2004-11-16 Engelhard Corporation Stable slurries of catalytically active materials
US6863984B2 (en) 1995-01-20 2005-03-08 Engelhard Corporation Catalyst and adsorption compositions having improved adhesion characteristics
US20050074382A1 (en) * 1995-08-07 2005-04-07 Giorgio Vergani Method for deoxygenating ammonia with reduced oxides of iron and manganese
KR100918105B1 (en) 2008-03-27 2009-09-22 한국화학연구원 Catalysts for fischer-tropsch synthesis on cobalt/zirconium-phosphorus/silicon dioxide and preparation methods thereof
US20100209324A1 (en) * 2009-02-16 2010-08-19 Millennium Inorganic Chemicals, Inc. Catalyst Promoters in Vanadium-Free Mobile Catalyst
US7955418B2 (en) 2005-09-12 2011-06-07 Abela Pharmaceuticals, Inc. Systems for removing dimethyl sulfoxide (DMSO) or related compounds or odors associated with same
WO2012066295A1 (en) * 2010-11-17 2012-05-24 Steritrox Limited Ozone decomposition catalyst for use in a sterilisation and/or decontamination process
US8435224B2 (en) 2005-09-12 2013-05-07 Abela Pharmaceuticals, Inc. Materials for facilitating administration of dimethyl sulfoxide (DMSO) and related compounds
US8480797B2 (en) 2005-09-12 2013-07-09 Abela Pharmaceuticals, Inc. Activated carbon systems for facilitating use of dimethyl sulfoxide (DMSO) by removal of same, related compounds, or associated odors
US8673061B2 (en) 2005-09-12 2014-03-18 Abela Pharmaceuticals, Inc. Methods for facilitating use of dimethyl sulfoxide (DMSO) by removal of same, related compounds, or associated odors
US9427419B2 (en) 2005-09-12 2016-08-30 Abela Pharmaceuticals, Inc. Compositions comprising dimethyl sulfoxide (DMSO)
US9839609B2 (en) 2009-10-30 2017-12-12 Abela Pharmaceuticals, Inc. Dimethyl sulfoxide (DMSO) and methylsulfonylmethane (MSM) formulations to treat osteoarthritis
WO2019110968A1 (en) * 2017-12-04 2019-06-13 Ricardo Uk Limited Pollutant treatment process and apparatus
CN112958088A (en) * 2021-03-23 2021-06-15 河南神马尼龙化工有限责任公司 Preparation method of biochar catalyst for synergistically purifying volatile organic pollutants

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4914072A (en) * 1988-03-02 1990-04-03 Texaco Inc. Phosphorus/titania/zirconia catalyst for preparation of linear polyethylenepolyamines
US5192452A (en) * 1988-07-12 1993-03-09 Nippon Shokubai Kagaku Kogyo, Co., Ltd. Catalyst for water treatment
KR940006404B1 (en) * 1988-07-12 1994-07-20 닛뽕쇼꾸바이가가꾸 고오교가부시끼가이샤 Catalyst for treatment of water
JPH02187148A (en) * 1988-10-31 1990-07-23 Sakai Chem Ind Co Ltd Catalyst for decomposing ozone
EP0371740B1 (en) * 1988-11-28 1993-09-22 Sakai Chemical Industry Co., Ltd., Catalyst and method for ozone decomposition
US5221649A (en) * 1988-11-28 1993-06-22 Sakai Chemical Industry Co., Ltd. Catalysts and methods for ozone decomposition
EP0387044A1 (en) * 1989-03-07 1990-09-12 Sakai Chemical Industry Co., Ltd., Catalyst and method for ozone decomposition
US7150861B2 (en) 2001-09-28 2006-12-19 Nippon Shokubai Co., Ltd. Catalyst for purification of exhaust gases and process for purification of exhaust gases
ATE458543T1 (en) * 2003-10-15 2010-03-15 Haldor Topsoe As CATALYST SUPPORT, CATALYST MADE THEREFROM AND PROCESS FOR PURIFYING EXHAUST GASES
FR2897000B1 (en) * 2006-02-06 2009-10-23 Degremont Sa CATALYTIC PROCESS FOR THE PURIFICATION OF GASES.
GB0822479D0 (en) * 2008-12-10 2009-01-14 Johnson Matthey Plc Improvements in catalysts
EP3062925B1 (en) 2013-10-30 2022-07-13 BASF Corporation Catalyst coatings for pollution control
CN109364913A (en) * 2018-11-09 2019-02-22 南京工业大学 A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst and its preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5387972A (en) * 1977-01-12 1978-08-02 Takeda Chem Ind Ltd Ozone removing method
US4173549A (en) * 1978-09-22 1979-11-06 Dart Industries Inc. Catalyst composition for decomposing ozone
GB2056424A (en) * 1979-08-08 1981-03-18 Johnson Matthey Co Ltd Decomposition of ozone

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018706A (en) * 1975-07-21 1977-04-19 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalysts for purifying exhaust and waste gases
GB2002648B (en) * 1977-08-05 1982-05-26 Johnson Matthey Co Ltd Catalyst
JPS5654206A (en) * 1979-10-03 1981-05-14 Xerox Corp High porous catalyst supporting body for ozone removing device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5387972A (en) * 1977-01-12 1978-08-02 Takeda Chem Ind Ltd Ozone removing method
US4173549A (en) * 1978-09-22 1979-11-06 Dart Industries Inc. Catalyst composition for decomposing ozone
GB2056424A (en) * 1979-08-08 1981-03-18 Johnson Matthey Co Ltd Decomposition of ozone

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5472676A (en) * 1989-05-11 1995-12-05 Nippon Shokubai Co., Ltd. Method of deodorizing a gas containing maloderous components
US5683532A (en) * 1990-08-12 1997-11-04 Kabushiki Kaisha Seibu Giken Method of manufacturing an active silica gel honeycomb adsorbing body usable in an atmosphere having 100% relative humidity
US5829066A (en) * 1990-11-19 1998-11-03 Takeda Chemical Industries, Ltd. Deodorizing apparatus and a toilet provided with the apparatus
US5212140A (en) * 1991-02-28 1993-05-18 Sakai Chemical Industry Co., Inc. Catalyst for decomposing ozone
US5403548A (en) * 1992-02-28 1995-04-04 Takeda Chemical Industries Ltd. Activated carbon adsorbent and applications thereof
US5422331A (en) * 1994-02-25 1995-06-06 Engelhard Corporation Layered catalyst composition
US5620672A (en) * 1994-02-25 1997-04-15 Engelhard Corporation Layered catalyst composition
US6863984B2 (en) 1995-01-20 2005-03-08 Engelhard Corporation Catalyst and adsorption compositions having improved adhesion characteristics
US6517899B1 (en) 1995-01-20 2003-02-11 Engelhard Corporation Catalyst and adsorption compositions having adhesion characteristics
US6616903B2 (en) 1995-01-20 2003-09-09 Engelhard Corporation Method and apparatus for treating the atmosphere
US6200542B1 (en) 1995-01-20 2001-03-13 Engelhard Corporation Method and apparatus for treating the atmosphere
US6214303B1 (en) 1995-01-20 2001-04-10 Engelhard Corporation Method and apparatus for treating the atmosphere
US6340066B1 (en) 1995-01-20 2002-01-22 Engelhard Corporation Pollutant treating devices and methods of making the same
US20030166466A1 (en) * 1995-01-20 2003-09-04 Hoke Jeffrey B. Catalyst and adsorption compositions having improved adhesion characteristics
US6818254B1 (en) 1995-01-20 2004-11-16 Engelhard Corporation Stable slurries of catalytically active materials
US7011799B2 (en) * 1995-08-07 2006-03-14 Saes Getters S.P.A. Method for deoxygenating ammonia with reduced oxides of iron and manganese
US20050074382A1 (en) * 1995-08-07 2005-04-07 Giorgio Vergani Method for deoxygenating ammonia with reduced oxides of iron and manganese
US5849256A (en) * 1996-04-26 1998-12-15 Engelhard Corporation Method for oxidizing carbon monoxide in a gas stream containing oxidizable sulphur compounds
US5997831A (en) * 1996-07-12 1999-12-07 Engelhard Corporation Method of catalytically treating the atmosphere and heat exchange devices produced thereby
US6586359B1 (en) 1998-03-23 2003-07-01 Engelhard Corporation Catalytic material for treating pollutant-containing gases
US6156283A (en) * 1998-03-23 2000-12-05 Engelhard Corporation Hydrophobic catalytic materials and method of forming the same
US6685898B2 (en) 1998-03-23 2004-02-03 Engelhard Corporation Hydrophobic catalytic materials and method of forming the same
US6375904B1 (en) 1999-12-20 2002-04-23 Airtex Manufacturing, Inc. Wastewater collection system gas emission control
US20040156767A1 (en) * 2001-04-12 2004-08-12 Industrial Technology Research Institute Process and apparatus for treating contaminated gas
US6911190B2 (en) 2001-04-12 2005-06-28 Industrial Technology Research Institute Process and apparatus for treating contaminated gas
US6712879B2 (en) * 2001-09-28 2004-03-30 Kabushiki Kaisha Toshiba Carbon dioxide gas absorbent and carbon dioxide gas separating apparatus
US6838065B2 (en) * 2003-01-28 2005-01-04 Industrial Technology Research Institute Method and apparatus for treating waste gas containing PFC and/or HFC
US20040146442A1 (en) * 2003-01-28 2004-07-29 Shu-Sung Lin Method and apparatus for treating waste gas containing PFC and/or HFC
US9186297B2 (en) 2005-09-12 2015-11-17 Abela Pharmaceuticals, Inc. Materials for facilitating administration of dimethyl sulfoxide (DMSO) and related compounds
US8673061B2 (en) 2005-09-12 2014-03-18 Abela Pharmaceuticals, Inc. Methods for facilitating use of dimethyl sulfoxide (DMSO) by removal of same, related compounds, or associated odors
US7955418B2 (en) 2005-09-12 2011-06-07 Abela Pharmaceuticals, Inc. Systems for removing dimethyl sulfoxide (DMSO) or related compounds or odors associated with same
US9427419B2 (en) 2005-09-12 2016-08-30 Abela Pharmaceuticals, Inc. Compositions comprising dimethyl sulfoxide (DMSO)
US9186472B2 (en) 2005-09-12 2015-11-17 Abela Pharmaceuticals, Inc. Devices for removal of dimethyl sulfoxide (DMSO) or related compounds or associated odors and methods of using same
US8298320B2 (en) 2005-09-12 2012-10-30 Abela Pharmaceuticals, Inc. Systems for removing dimethyl sulfoxide (DMSO) or related compounds, or odors associated with same
US8435224B2 (en) 2005-09-12 2013-05-07 Abela Pharmaceuticals, Inc. Materials for facilitating administration of dimethyl sulfoxide (DMSO) and related compounds
US8440001B2 (en) 2005-09-12 2013-05-14 Abela Pharmaceuticals, Inc. Systems for removing dimethyl sulfoxide (DMSO) or related compounds, or odors associated with same
US8480797B2 (en) 2005-09-12 2013-07-09 Abela Pharmaceuticals, Inc. Activated carbon systems for facilitating use of dimethyl sulfoxide (DMSO) by removal of same, related compounds, or associated odors
KR100918105B1 (en) 2008-03-27 2009-09-22 한국화학연구원 Catalysts for fischer-tropsch synthesis on cobalt/zirconium-phosphorus/silicon dioxide and preparation methods thereof
US20100209324A1 (en) * 2009-02-16 2010-08-19 Millennium Inorganic Chemicals, Inc. Catalyst Promoters in Vanadium-Free Mobile Catalyst
US8148295B2 (en) * 2009-02-16 2012-04-03 Millennium Inorganic Chemicals, Inc. Catalyst promoters in vanadium-free mobile catalyst
US9839609B2 (en) 2009-10-30 2017-12-12 Abela Pharmaceuticals, Inc. Dimethyl sulfoxide (DMSO) and methylsulfonylmethane (MSM) formulations to treat osteoarthritis
US9855212B2 (en) 2009-10-30 2018-01-02 Abela Pharmaceuticals, Inc. Dimethyl sulfoxide (DMSO) or DMSO and methylsulfonylmethane (MSM) formulations to treat infectious diseases
US10596109B2 (en) 2009-10-30 2020-03-24 Abela Pharmaceuticals, Inc. Dimethyl sulfoxide (DMSO) or DMSO and methylsulfonylmethane (MSM) formulations to treat infectious diseases
WO2012066295A1 (en) * 2010-11-17 2012-05-24 Steritrox Limited Ozone decomposition catalyst for use in a sterilisation and/or decontamination process
WO2019110968A1 (en) * 2017-12-04 2019-06-13 Ricardo Uk Limited Pollutant treatment process and apparatus
US10780395B2 (en) 2017-12-04 2020-09-22 Ricardo Inc. Pollutant treatment process and apparatus
US11305231B2 (en) 2017-12-04 2022-04-19 Ricardo Uk Limited Pollutant treatment process and apparatus
CN112958088A (en) * 2021-03-23 2021-06-15 河南神马尼龙化工有限责任公司 Preparation method of biochar catalyst for synergistically purifying volatile organic pollutants

Also Published As

Publication number Publication date
ES2033838T3 (en) 1993-04-01
DE3781134D1 (en) 1992-09-17
EP0275620A3 (en) 1989-02-22
KR880008830A (en) 1988-09-13
EP0275620B1 (en) 1992-08-12
EP0275620A2 (en) 1988-07-27
DE3781134T2 (en) 1993-04-08

Similar Documents

Publication Publication Date Title
US5145657A (en) Method for purification of gas
US5430230A (en) Method for disposing of organohalogen compounds by oxidative decomposition
JPH064126B2 (en) Exhaust gas purification method
KR100469005B1 (en) Photocatalytic system for the removal of volatile organic compounds
WO1996020786A1 (en) Catalyst for purifying fumigation exhaust gas and purification method of fumigation exhaust gas
JP2001187343A (en) Cleaning catalyst at normal temperature and utilization thereof
JPH0510973B2 (en)
KR20210106509A (en) Catalyst for ammonia decomposition and treatment method of exhaust gas
JP2001104728A (en) Bag filter and exhaust gas cleaning method
JP3604740B2 (en) Ozone decomposition catalyst and ozone decomposition method
JPH0741146B2 (en) Deodorization method
JP3546766B2 (en) Deodorizing catalyst
JP2002263449A (en) Activated carbon filter
JP2001104781A (en) Material for removing nitrogen oxide and method for removing it
JPH0741169B2 (en) Air oxidation removal method of malodorous substance
JPH0585218B2 (en)
JPH0371903B2 (en)
JPH04222631A (en) Ozone decomposing catalyst
JPH057776A (en) Catalyst and its manufacture
JPH04231059A (en) Method for deodorizing
JPH0528148B2 (en)
JPH0586253B2 (en)
JPH0616849B2 (en) Catalyst for treating gas containing harmful and odorous components
JP2002079080A (en) Aldehydes adsorbing and decomposing agent and its production method
JPH08215575A (en) Catalyst for purification of exhaust gas containing nitrogen oxide and method for purifying the same

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 20000908

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362